KR101931789B1 - Compositions and articles of manufacture containing branched polycarbonate - Google Patents

Abstract

A polycarbonate-containing composition comprising a maximum melt viscosity of at least 8,000 poise, as measured using a parallel plate melt rheology test at a temperature of from about 350 DEG C to about 450 DEG C at a heating rate of 10 DEG C / min, Polycarbonate containing compositions having a UL94 V0 rating at a thickness of 1.0 mm, 1.5 mm, 2.0 mm, or 1.0 mm to 2.0 mm are disclosed.

Description

[0001] Compositions and articles containing branched polycarbonate [0002]

This disclosure relates to polycarbonate compositions, and in particular to endcapped polycarbonate compositions, methods of manufacture, and uses thereof.

Polycarbonate is a high performance plastic with excellent impact strength (ductility). However, polycarbonate often has a relatively limited fluidity required for the manufacture of thin walled articles. Medium to high flow polycarbonate grades are problematic in that low temperature ductility is sacrificed for better flow. In addition, polycarbonate compositions often require the use of flame retardants often for successful use in the manufacture of various articles and components.

Accordingly, there remains a need in the art for high-throughput polycarbonate compositions and articles made therefrom, which can be applied to articles of acceptable transparency and flame retardancy in industry, in particular for thin wall applications of 25,000 poise, for example 1.5 mm < / RTI > thickness.

The present invention provides a composition comprising: a flame retardant and a polycarbonate comprising formula (1)

(1)

(One)

At least 60% of the total number of R < ¹ > groups contains an aromatic organic group and the remainder is an aliphatic, alicyclic or aromatic group; Wherein the polycarbonate comprises a terminal capping agent, the terminal capping agent is not cyanophenol; Wherein the polycarbonate comprises a branching agent and an end capping agent; The composition has a peak melt viscosity of greater than 8,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10 DEG C / min at a temperature of from about 350 DEG C to about 450 DEG C; The molded article of the composition has a UL94 VO rating at a thickness of 1 mm, 1.5 mm, 2.0 mm, or 1.0 mm to 2.0 mm.

In another embodiment, the maximum melt viscosity is greater than 7,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10 占 폚 / min at a temperature of from about 350 占 폚 to about 450 占 폚.

In another embodiment, the composition has a maximum melt viscosity of greater than 25,000 poise, as measured using a parallel plate melt rheology test at a heating rate of 10 DEG C / min at a temperature of from about 350 DEG C to about 450 DEG C, The molded article of the composition can achieve a UL94 VO rating at a thickness of 1.5 mm, 2.0 mm, or 1.0 mm to 2.0 mm.

The present invention also provides a composition comprising: a flame retardant and a polycarbonate comprising formula (1):

(1)

(One)

At least 60% of the total number of R < ¹ > groups contains an aromatic organic group and the remainder is an aliphatic, alicyclic or aromatic group; Wherein the polycarbonate comprises a terminal capping agent, wherein the terminal capping agent is selected from the group consisting of phenol; At least one alkyl group, an alkoxy group, an ester group, an ether group, or a phenol substituted with a halogen; Wherein the polycarbonate comprises a branching agent selected from one or more of THPE, TMTC, isatin-bis-phenol, The fraction of the polycarbonate is greater than about 1%; The molecular weight of the polycarbonate is from about 20,000 g / mole to about 40,000 g / mole; The end capping agent has a pKa of about 8.3 to about 11; Said flame retardant comprises potassium perfluorobutanesulfonate and optionally does not comprise a chlorine or bromine containing composition; The polycarbonate containing the branching agent and the endcapping agent has a maximum melt viscosity of greater than 8,000 poise, as measured using a parallel plate melt rheology test at a heating rate of 10 DEG C / min at a temperature of from about 350 DEG C to about 450 DEG C Lt; / RTI > The molded article of the composition has a UL94 VO rating at a thickness of 1.0 mm, 1.5 mm, 2.0 mm, or 1.0 mm to 2.0 mm.

In a further embodiment, the maximum melt viscosity is greater than 25,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10 占 폚 / min at a temperature of from about 350 占 폚 to about 450 占 폚.

The present invention further provides a method of making a product having a UL94 VO rating in a thickness of 1.5 mm to 2 mm comprising the following steps: (a) providing a polycarbonate, said polycarbonate having the formula (1):

(1)

(One)

(Wherein at least 60% of the total number of R < ¹ > groups contain aromatic organic groups, the remainder being aliphatic, cycloaliphatic, or aromatic groups); End capping agent; And a polycarbonate comprising a branching agent; (b) a step of selecting the terminal capping agent, based on the molecular weight and the branching agent of branching given by the polycarbonate, and the MVR is in the range of about 1 to about 15 cm ^3/10 min of the polycarbonate, the Wherein the pKa of the end capping agent is from about 8.3 to about 11; (c) forming a polycarbonate containing the end capping agent and the branching agent, wherein the polycarbonate is subjected to a parallel plate melt rheology test at a heating rate of 10 DEG C / min at a temperature of from about 350 DEG C to about 450 DEG C Having a maximum melt viscosity of at least 8,000 poises, as measured using the method of the present invention; And (d) blending the flame retardant with the polycarbonate formed.

In a further embodiment, the maximum melt viscosity is greater than 25,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10 占 폚 / min at a temperature of from about 350 占 폚 to about 450 占 폚.

The present invention further provides a composition comprising: a flame retardant; And a polycarbonate comprising the formula (1):

(1)

(One)

At least 60% of the total number of R < ¹ > groups contains an aromatic organic group and the remainder is an aliphatic, alicyclic or aromatic group; Wherein the polycarbonate contains at least one bisphenol; Wherein the polycarbonate comprises a non-cyanophenol end capping agent; Said polycarbonate comprising a branching agent; The polycarbonate containing the branching agent and the end capping agent has a maximum melt viscosity of at least 7,000 posie as calculated from the maximum solubility viscosity equation; -57135.91 + 36961.39 * BL + 14001.13 * MW 1/3 - 46944.24 * pKa - 322.51 * BL * MW 1/3 - 2669.19 * BL * pKa + 215.83 * MW 1/3 * pKa + 1125.63 * BL 2 - 200.11 * MW ^{2/3 + 2231.15 * pKa 2} , where, BL is the molar ratio of branching agent in the formulation, which is determined by dividing the total number of moles of the bisphenol or bisphenol used in the composition the number of moles of the branching agent, the MW is the branching agent and the distal The weight average molecular weight of said polycarbonate containing a capping agent, said weight average molecular weight being determined by gel permeation chromatography using a polycarbonate standard, wherein said pKa is the pKa of said endcapping agent; The molded article of the composition has a UL94 VO rating at a thickness of 1 mm, 1.5 mm, 2.0 mm, or 1.0 mm to 2.0 mm.

In a further embodiment, the maximum melt viscosity is greater than 25,000 poise as calculated from the above equation.

The present invention further provides a method of making a product having a UL94 VO rating in the thickness of 1.5 mm to 2 mm, comprising the steps of: (a) providing a polycarbonate, said polycarbonate having the formula (1) :

(1)

(One)

(Wherein at least 60% of the total number of R < ¹ > groups contains aromatic organic groups and the remainder is an aliphatic, alicyclic or aromatic group, the polycarbonate containing at least one bisphenol); As the end capping agent, a non-cyanophenol end capping agent; And a polycarbonate comprising a branching agent; (b) a step of selecting the terminal capping agent, based on the molecular weight and the branching agent of branching given by the polycarbonate, and the MVR is in the range of about 1 to about 15 cm ^3/10 min of the polycarbonate, the Wherein the end capping agent has a pKa of from about 8 to about 11; (c) forming a polycarbonate containing the end capping agent and the branching agent, wherein the polycarbonate has a maximum melt viscosity of at least 7,000 poise, as calculated by the following maximum melt viscosity equation: -57135.91 + 36961.39 ^{* BL + 14001.13 * MW 1/} 3 - 46944.24 * pKa - 322.51 * BL * MW 1/3 - 2669.19 * BL * pKa + 215.83 * MW 1/3 * pKa + 1125.63 * BL 2 - 200.11 * MW 2/3 + 2231.15 * pKa ² , where BL is the mole ratio of branching agent in the blend, determined by dividing the number of moles of branching agent by the total number of moles of bisphenol or bisphenols in the composition, wherein MW is the weight average molecular weight of the polycarbonate formed , The weight average molecular weight is determined by gel permeation chromatography using a polycarbonate standard, wherein pKa is the pKa of the end capping agent; And (d) blending the flame retardant with the polycarbonate formed.

In a further embodiment, the maximum melt viscosity is greater than 25,000 poise as calculated from the above equation.

Figure 1 graphically illustrates temperature gradient data for three different polycarbonates containing different end capping agents, branching and MW (weight average molecular weight) values. This graph was obtained using a dynamic rheological test with parallel plate fixtures. The maximum melt viscosity values were obtained using these and similar graphs.

The word " about " should be taken in a conventional and familiar sense, and it should be about the word or phrase (s) that it is modifying. Within the context of pKa, the word " about " associated with pKa may be the same value as that number or it may be equal to a value in the range of +/- 0.1 pKa units. For example, a pKa of about 8.3 may include 8.2. The word " drug " associated with a branching agent may be the same value as that number or may be equal to a value in the range of +/- 0.05% of the branching. For example, about 1% may include 0.95%. Within the context of pKa and branching, the description of the word " about " does not limit the conventional and familiar meaning of the word " about " to other terms / numerical values modifying the word " about. "

Polycarbonate standards refer to polycarbonate resins with molecular weights that are considered reliable and verified by various analytical methods. This is used to calibrate the gel permeation chromatography molecular weight measurement method.

As described above, the present invention provides a composition comprising:

A flame retardant and polycarbonate comprising the formula (1):

(1)

(One)

Wherein at least 60% of the total number of R < ¹ > groups contain aromatic organic groups, the remainder being aliphatic, alicyclic, or aromatic groups; Wherein the polycarbonate comprises a terminal capping agent, the terminal capping agent is not cyanophenol; Wherein the polycarbonate comprises a branching agent and a terminal capping agent and wherein the composition has a viscosity of at least 8,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10 [deg.] C / min at a temperature of from about 350 [ Has a maximum melt viscosity; The molded article of the composition has a UL94 VO rating at a thickness of 1 mm, 1.5 mm, 2.0 mm, or 1.0 mm to 2.0 mm.

A. Polycarbonate Material / Structural Backbone of the Composition

Various types of polycarbonates include the formula (1): < RTI ID = 0.0 >

(1)

(One)

Wherein at least 60% of the total number of R < ¹ > groups contain aromatic organic groups, the remainder being aliphatic, cycloaliphatic, and / or aromatic groups, which are used in the claimed invention / .

The choice of polycarbonate backbone depends on various factors such as end use and other factors understood by those skilled in the art.

In one embodiment, the polycarbonate comprises formula (1):

(1)

(One)

Wherein at least 60% of the total number of R < ¹ > groups contains aromatic organic groups, the remainder being aliphatic, cycloaliphatic, and / or aromatic groups.

In another embodiment, the polycarbonate is derived from bisphenol A.

In another embodiment, each R < ^{1 >} group is a divalent aromatic group and is derived, for example, from an aromatic dihydroxy compound of formula (2)

HO-R < ¹ > -OH (2)

Wherein at least 60% of the total number of R < ¹ > groups contains aromatic organic groups, the remainder being aliphatic, cycloaliphatic, and / or aromatic groups.

In another embodiment, each R < ^{1 >} group is a divalent aromatic group and is derived, for example, from an aromatic dihydroxy compound of formula (3)

HO-A ¹ -Y ¹ -A ² -OH (3)

Wherein A ¹ and A ² are each independently a single ring divalent arylene group and Y ¹ is a single bond or a linking group having one or two atoms separating A ¹ from A ² . In an exemplary embodiment, one atom separates A ¹ from A ² . In other embodiments, each A ¹ and A ² is phenylene, and Y ¹ is in the para position of each hydroxyl group on the phenylene. Exemplary non-limiting examples of this type of group are -O-, -S-, -S (O) -, -S (O) _2- , -C (O) -, methylene, cyclohexyl- - [2.2.1] -cycloheptylidene, ethylidene, isopropylidene, neopentylidene, cyclohexylidene, cyclopentadecylidene, cyclododecylidene, and adamantylidene. The linking group Y < ¹ > may be a hydrocarbon group such as methylene, cyclohexylidene, or isopropylidene or a saturated hydrocarbon group.

The bisphenol compounds of formula (4) are included within the range of formula (3).

(4)

(4)

Here, R ^a and R ^b each independently represent a hydrogen atom, a halogen atom, a C _{1 -12} alkyl, or a monovalent hydrocarbon group, and may be the same or different; p and q are each independently an integer of 0 to 4; X ^a represents a single bond, C _{3 -20} cycloalkylidene, or one of the groups of formula (5) or (6)

(5)

(6)

(5)

(6)

Wherein R ^c and R ^d are each independently hydrogen, C _{1 -12} alkyl, C _{1 -12-cycloalkyl,} C _{7 -12} aryl, C _{1 -12} alkyl, heterocyclic, cyclic C _{7 -12,} or heteroarylalkyl, or R ^c and R ^d denotes taken so C _{3 -20} cyclic alkyl group or a C _{3 -20-containing} cyclic alkylene group having a heteroatom containing a hetero atom and a carbon atom with two or more atoms, R 2 ^e is Is a C _{1 -12} hydrocarbon group. In particular, R ^c and R ^d are each the same hydrogen or C _{1 -4} alkyl group, specifically the same C _{1 -3} alkyl group, more particularly methyl.

In one embodiment, R ^c and R ^d are taken so C _{3 -20} represents cyclic alkyl group or a C _{3 -20-containing} cyclic alkylene group heteroatom-containing carbon atom and a hetero atom having two or more atoms with . These groups may be in the form of mono-saturated or unsaturated rings or in the form of a fused multicyclic ring system, wherein the fused ring is saturated, unsaturated, or aromatic. Particular heteroatom-containing cyclic alkylene groups include at least one heteroatom having at least two valences and at least two carbon atoms. Exemplary hetero atoms in the cyclic alkyl group containing a hetero atom is -O-, -S-, and -N (Z) - comprises a, in which Z is hydrogen, hydroxy, C _{1 -12} alkyl, C _{1 -12} Alkoxy, or C _1-12 acyl.

In a specific exemplary embodiment, X ^a is a substituted C _{3 -18} cycloalkyl alkylidene of formula (7):

(7)

(7)

^R wherein R, R ^p, R ^q, and R ^t are each independently hydrogen, halogen, oxygen, or C _{1 -12} alkyl, with the proviso that, where ^{R r, R p, R q} , and R ^t 2 out of the above May be taken together to form a fused alicyclic, aromatic, or heteroaromatic ring; I is a direct bond, carbon, divalent oxygen, sulfur, or -N (Z) -, where Z is hydrogen, halogen, hydroxy, C _{1 -12} alkyl, C _{1 -12} alkyl, or C _{1 -12} acyl ; h is 0 to 2, j is 1 or 2, i is an integer of 0 or 1, and k is an integer of 0 to 3. When the bond ring is aromatic it will be understood that the ring indicated in formula (7) will have an unsaturated carbon-carbon bond at the junction of the ring. when i is 0 and k is 1, the ring represented by the formula (7) contains 4 carbon atoms, and when i is 0 and k is 2, the indicated ring contains 5 carbon atoms, i is 0 And when k is 3, the ring contains 6 carbon atoms. In one embodiment, two adjacent groups (e. G., R ^q and R ^t taken together) form one aromatic group, and in another embodiment R ^q and R ^t taken together to form one Form an aromatic group and R < ^r > and R < ^p > taken together to form a second aromatic group.

When k is 3 and i is 0, for example, bisphenols containing substituted or unsubstituted cyclohexane units such as the bisphenols of formula (8) are used:

(8)

(8)

Here, R ^p, R ^q, and R ^t are each independently hydrogen, halogen, oxygen, or C _{1 -12} alkyl, with the proviso that, where R ^p, R ^q, and R ^t R ^a and R ^b are each independently a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group, and p and q are each independently a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group, Are each independently an integer of 0 to 4, and j is 1 or 2. In one embodiment, R ^p, R ^q, and R ^t are each independently hydrogen, C _{1 -12} alkyl, or halogen; Each R ^a and R ^b is independently hydrogen or C _1-12 alkyl. R ^p , R ^q , and R ^t If one or more of a C _{1 -12} alkyl, C _{1 -12} alkyl may be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated or unsaturated. Such cyclohexane-containing bisphenols, for example, reaction products of 2 moles of phenol and 1 mole of hydrogenated isophorone are useful in the production of polycarbonate polymers having a high glass transition temperature and a high heat distortion temperature. Polycarbonate containing cyclohexyl bisphenol, or a combination comprising at least one of the foregoing and another bisphenol polycarbonate is supplied by Bayer under the trade name APEC ^** .

Other useful dihydroxy compounds having formula (2) include aromatic dihydroxy compounds of formula (9):

HO-R < ¹ > -OH (2)

(9)

(9)

Wherein, R ^h are each independently a halogen atom, halogen-substituted C _{1 -10} dihydro car invoking such as C _{1 -10} dihydro car pray, a halogen-substituted C _{1 -10} alkyl, such as C _{1 -10} alkyl, n is 0 < / RTI > Halogen is typically bromine.

Some illustrative examples of dihydroxy compounds include: 4,4'-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, bis (4-hydroxy Phenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) phenyl methane, 2,2-bis Bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1- Bis (4-hydroxyphenyl) isobutene, 1,1-bis (4-hydroxyphenyl) cyclododecane, trans- Bis (4-hydroxyphenyl) toluene, bis (4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-ethyl- (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl- Bis (4-hydroxyphenyl) propane, 2,1-bis (3-methoxy-4-hydroxyphenyl) propane, Dibromo-2,2-bis (4-hydroxyphenyl) ethylene, 1,1-dichloro-2,2-bis (5-phenoxy (4-hydroxyphenyl) ethylene, 4,4'-dihydroxybenzophenone, 3,3-bis (4-hydroxyphenyl) -1,6-hexanedione, ethylene glycol bis (4-hydroxy Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Hydroxyphenyl) fluorine, 2,7-dihydroxypyrene, 6,6'-dihydroxy-3,3,3 ', 3'-tetramethylspiro (bis) indane ("spirobiindane bisphenol" , 3,3-bis (4-hydroxyphenyl) phthalide, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxyphenoxathine , 2,7-dihydroxy-9,10-dimethylphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and 2,7-dihydroxycarbazole 5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-methyl resorcinol, 5-ethyl resorcinol, - cumyl resorcinol, 2,4,5,6-tetrafluororesorcinol, 2,4,5,6-tetrabromorezone A substituted resorcinol compound such as sinol; Catechol; Hydroquinone; Methylhydroquinone, 2-ethylhydroquinone, 2-propylhydroquinone, 2-butylhydroquinone, 2-t-butylhydroquinone, 2-phenylhydroquinone, 2-cumylhydroquinone, Tetramethylhydroquinone, 2,3,5,6-tetra-t-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromohydroquinone Substituted hydroquinone; As well as at least one of the above dihydroxy compounds.

Specific examples of bisphenol compounds that can be represented by the formula (3) include 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Bis (4-hydroxyphenyl) propane (hereinafter, referred to as "bisphenol A" or "BPA"), 2,2- Bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) n-butane, 2,2- Phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine (PPPBP), 3-hydroxy- , And 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane (DMBPC). Combinations comprising at least one of the above dihydroxy compounds may also be used.

As used herein, the term " polycarbonate " includes homopolycarbonates, copolymers containing different R ¹ moieties in the carbonate (referred to herein as " copolycarbonates "), and other types such as carbonate units and ester units Of a polymeric unit. In a specific embodiment, the polycarbonate is a linear homopolymer or copolymer comprising units derived from bisphenol A, wherein each of A ¹ and A ³ in formula (3) is p-phenylene and Y ¹ is Isopropylidene. More specifically, in this embodiment, at least 60%, especially at least 80%, of the R < ^{1 >} groups in the polycarbonate are derived from bisphenol A.

Another specific type of copolymer is a polyester carbonate, also known as a polyester-polycarbonate. Such a copolymer further contains a repeating unit of the formula (10) in addition to the repeating carbonate chain unit of the formula (1)

(10)

(10)

G., Where D is a divalent group and, for example, derived from a dihydroxy compound, there C _2-10 alkylene groups, C _{6 -20} alicyclic group, C _{6 -20} aromatic group or a polyoxyalkylene can alkylene group, wherein alkylene Group contains 2 to 6 carbon atoms, specifically 2, 3 or 4 carbon atoms; T is a divalent group derived from a dicarboxylic acid, for example, _-10 C ₂ alkyl group, a C ₆ alicyclic group _{-20, -20} C ₆ alkyl, an aromatic group, C _{6 -30} aryl group, or a C _{6 - 20} aromatic group.

In one embodiment, D is a C _{2 -30} alkylene group having a linear, branched, or cyclic (including multiple ring) structure. In another embodiment, D is derived from an aromatic dihydroxy compound of formula (4). In another embodiment, D is derived from an aromatic dihydroxy compound of formula (9).

Examples of aromatic dicarboxylic acids that can be used to prepare the polyester units are isophthalic acid or terephthalic acid, 1,2-di (p-carboxyphenyl) ethane, 4,4'-dicarboxy diphenyl ether, '- bisbenzoic acid, and combinations comprising at least one of the foregoing acids. Acids containing conjugated rings such as in 1,4-, 1,5-, or 2,6-naphthalene dicarboxylic acids may also be present. Specific dicarboxylic acids are terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexanedicarboxylic acid, or a combination thereof. The specific dicarboxylic acid comprises a combination of isophthalic acid and terephthalic acid wherein the weight ratio of isophthalic acid to terephthalic acid is 91: 9 to 2:98. In another specific embodiment, D is a C _{2 -6} alkylene group and T is p-phenylene, m-phenylene, naphthalene, a divalent cycloaliphatic group, or a combination thereof. This type of polyester includes poly (alkylene terephthalate).

The molar ratio of ester units to carbonate units in the copolymer can vary widely, for example from 1:99 to 99: 1, in particular from 10:90 to 90:10, more specifically from 25:75 to 75:25 , Depending on the desired properties of the final composition.

In a specific embodiment, the polyester units of the polyester-polycarbonate can be derived from the reaction of a combination of isophthalic diacid with terephthalic acid (or a derivative thereof) and resorcinol. In another specific embodiment, the polyester unit of the polyester-polycarbonate is derived from the reaction of bisphenol A with a combination of isophthalic acid and terephthalic acid. In a specific embodiment, the polycarbonate unit is derived from bisphenol A. In another specific embodiment, the polycarbonate units are derived from resorcinol and bisphenol A, wherein the molar ratio of resorcinol carbonate units to bisphenol A carbonate units is from 1:99 to 99: 1.

A specific example of the polycarbonate-polyester includes a polycarbonate having a carbonate unit of the formula (1), an ester unit of the formula (10), and a polysiloxane (also referred to herein as "polydiorganosiloxane") unit of the formula (11) Containing polysiloxane terpolymer is a copolycarbonate-polyester-polysiloxane terpolymer comprising:

(11)

(11)

Wherein R ^g are each independently C _{1 -13} alkyl, C _{1 -13} alkoxy group, a C _{2 -13} alkenyl, C _2-13 alkenyloxy group, C _{3 -6} cycloalkyl group, C _{3 -6} cycloalkoxy group, C _{6 -14} aryl group, a C _{6 -10} aryloxy group, a C _{7 -13} arylalkyl group, C _{7 -13} arylalkyl group, a C _{7 -13} alkyl, aryl, or C _{7 -13} alkyl aryloxy, above All of the groups may be wholly or partially halogenated with fluorine, chlorine, bromine, or iodine, or combinations thereof. Combinations of the above R &^lt; ^{g >} groups may be used in the same copolymer. In one embodiment, the polysiloxane comprises an R ^g with minimum hydrocarbon content. In a specific embodiment, the R ^g group with the minimum hydrocarbon content is a methyl group.

The E value in formula (11) can vary widely depending on the type and relative amount of each component in the thermoplastic composition, the desired properties of the composition, and similar considerations. In the present specification, E has an average value of 4 to 50. In one embodiment, E has an average value of 16 to 50, specifically 20 to 45, more specifically 25 to 45. In another embodiment, E has an average value of 4 to 15, specifically 5 to 15, more specifically 6 to 15, and even more specifically 7 to 12.

In one embodiment, the polydiorganosiloxane units are derived from dihydroxyaromatic compounds of formula (12):

(12)

(12)

Wherein E is as defined above; Each R ^g may be independently the same or different and is as defined above; Ar ^x may be independently the same or different and is a substituted or unsubstituted C _{6 -30} arylene group, and the bond is directly connected to the aromatic moiety. Suitable Ar ^x groups in formula (12) can be derived from C _{6 -30} dihydroxyaromatic compounds, for example dihydroxyaromatic compounds of formula (3), (4), (8) have. Combinations comprising at least one of the foregoing dihydroxyaromatic compounds may also be used. Exemplary dihydroxyaromatic compounds include resorcinol (i.e., 1,3-dihydroxybenzene), 4-methyl-1,3-dihydroxybenzene, 5-methyl-1,3-dihydroxybenzene, Dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- Bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) n-butane, 2,2- (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl sulfide), and 1,1-bis (4-hydroxy-t-butylphenyl) propane. Combinations comprising at least one of the foregoing dihydroxy compounds may also be used. In one embodiment, the dihydroxyaromatic compound is unsubstituted or substituted with a non-aromatic hydrocarbon containing substituent such as, for example, an alkyl, alkoxy, or alkylene substituent.

In a specific embodiment, when Ar ^x is derived from resorcinol, the polydiorganosiloxane repeat unit is derived from the dihydroxyaromatic compound of formula (13)

(13)

(13)

Alternatively, when Ar ^x is derived from bisphenol A, the polydiorganosiloxane repeat unit is derived from the dihydroxyaromatic compound of formula (14)

(14)

(14)

Wherein E is as defined above.

In another embodiment, the polydiorganosiloxane units are derived from dihydroxyaromatic compounds of formula (15):

(15)

(15)

Wherein R ^g and E are as defined above and R ² is each independently a divalent C _{1 -30} alkylene or C _{7 -30} arylene-alkylene, and the polymerized polysiloxane unit has a corresponding dihydroxyaromatic Is the reactive residue of the compound. In a specific embodiment, R ² is C _{7 -30} arylene-alkylene and the polydiorganosiloxane unit is derived from the dihydroxyaromatic compound of formula (16):

(16)

(16)

R ^g and E are as defined above. R ³ is a divalent C _{2 -8} aliphatic group each independently. M is each independently halogen, cyano, nitro, C _{1 -8} alkylthio, C _{1 -8} alkyl, C _{1 -8} alkoxy, C _{2 -8} alkenyl, C _{2 -8} alkenyloxy group, C _{3 -8} cycloalkyl, C _{3 -8} cycloalkoxy, C _{6 -10} aryl, C _{6 -10} aryloxy, C _{7 -12} arylalkyl, C _{7 -12} arylalkyl, C _{7 -12} alkyl, aryl, or C _7-12 alkyl Aryloxy, and f is each independently 0, 1, 2, 3, or 4.

In one embodiment, M is bromo or chloro; Alkyl groups such as methyl, ethyl, or propyl; An alkoxy group such as methoxy, ethoxy, or propoxy; Or an aryl group such as phenyl, chlorophenyl, or tolyl; R ³ is a dimethylene group, a trimethylene group or a tetramethylene group; R ^g is an aryl, such as a C _{1 -8} alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or phenyl, chlorophenyl or tolyl. In other embodiments, R ^g is methyl, or a combination of methyl and trifluoropropyl, or a combination of methyl and phenyl. In another embodiment, M is methoxy, n is 0 or 1, R ³ is a divalent C _{1 -3} aliphatic group, and R ^g is methyl.

In a specific embodiment, the polydiorganosiloxane units are derived from dihydroxyaromatic compounds of formula (17):

(17)

(17)

Wherein E is as defined above.

In another specific embodiment, the polydiorganosiloxane units are derived from dihydroxyaromatic compounds of formula (18):

(18)

(18)

Wherein E is as defined above.

The dihydroxypolysiloxane can typically be prepared by functionalizing a substituted siloxane oligomer of formula (19).

(19)

(19)

Wherein R ^g and E are as defined above and W is hydrogen, halogen (Cl, Br, I) or carboxylate. Exemplary carboxylates include acetates, formates, benzoates, and the like. In an exemplary embodiment, when W is H, the compound of formula (19) may be prepared by platinum catalysed addition with an aliphatic unsaturated monohydric phenol. Suitable aliphatic unsaturated monohydric phenols include, for example, eugenol, 2-allylphenol, 4-allylphenol, 4-allyl-2-methylphenol, 4- Allyl-2-allylphenol, 2-methyl-4-propylphenol, 2-allyl-4,6-dimethylphenol, 2- -Bromo-6-methylphenol, 2-allyl-6-methoxy-4-methylphenol, and 2-allyl-4,6-dimethylphenol. Combinations comprising one or more of the foregoing may also be used. When W is a halogen or a carboxylate, the functionalization may be carried out in the presence of a dihydroxyaromatic compound of formula (3), (4), (8), or (9) or a combination comprising at least one of the dihydroxyaromatic compounds described above ≪ / RTI > In an exemplary embodiment, the compound of formula (12) can be formed from alpha, omega-bisacetoxy polydiorganosiloxane and dihydroxyaromatic compounds under phase transition conditions.

In a specific embodiment, the copolycarbonate terpolymer comprises a polycarbonate unit of formula (1) wherein R ¹ is a C _{6 -30} arylene group, a polycarbonate unit derived from a siloxane diol of formula (14), (17) or (18) Polysiloxane units, and terpolymers having polyester units wherein T is a C _{6 -30} arylene group. In one embodiment, T is derived from isophthalic acid and / or terephthalic acid or reactive chemical equivalents thereof. In another embodiment, R < ¹ > is derived from a carbonate reaction product of resorcinol of formula (9) or a combination of a resorcinol of formula (9) and a bisphenol of formula (4).

The relative amounts of units of each type in the aforementioned terpolymers will vary depending on the properties of the desired terpolymer and are readily determined by those of ordinary skill in the art without undue experimentation using the guidance provided herein . For example, the polycarbonate-polyester-polysiloxane terpolymer may be present in an amount of from 0.1 to 25 wt% (wt%), specifically 0.2 to 10 wt%, based on the total weight of the polycarbonate-polyester-polysiloxane terpolymer, In an amount of from 0.2 to 6% by weight, more specifically from 0.2 to 5% by weight, even more specifically from 0.25 to 2% by weight, based on the total weight of the composition, with the proviso that the siloxane unit is a polycarbonate- Is provided by a covalently bonded polysiloxane unit in the polymer backbone of the polymer. The polycarbonate-polyester-polysiloxane terpolymer comprises from 0.1 to 49.85 wt% carbonate units, from 50 to 99.7 wt% ester units, and from 0.2 to 6 wt% polysiloxane units based on the total weight of polysiloxane units, ester units, and carbonate units Unit. ≪ / RTI > Alternatively, the polycarbonate-polyester-polysiloxane terpolymer may comprise from 0.25 to 2 wt% polysiloxane units, from 60 to 96.75 wt% ester units, and from 3.25 to 0.75 wt%, based on the total weight of polysiloxane units, ester units, And 39.75% by weight of carbonate units.

Various types of thermoplastic compositions are encompassed by the claimed invention / inventions encompassed by this disclosure.

In one embodiment, the polycarbonate is selected from one or more of the following: homopolycarbonate derived from bisphenol; Copolycarbonates derived from more than one bisphenol; And copolymers derived from one or more bisphenols and having one or more aliphatic ester units or aromatic ester units or siloxane units.

In another embodiment, in addition to the end-capped polycarbonate described above, the thermoplastic composition can also include other thermoplastic polymers, including, for example, polyesters; Polyamide; And other polycarbonate homopolymers and copolymers including polycarbonate-polysiloxane copolymers; And polyester carbonates, also known as polyester-polycarbonates; And polyesters. The polymer component of such a composition may comprise from 1 to 99% by weight, specifically from 10 to 90% by weight, more specifically from 20 to 80% by weight, of cyanophenyl-terminated polycarbonate, .

In another embodiment, a second polycarbonate is blended with the composition, and the second polycarbonate comprises formula (1):

(1)

(One)

The second polycarbonate differs from the polycarbonate in that at least 60% of the total number of R < ¹ > groups contains aromatic organic groups, the remainder being aliphatic, alicyclic or aromatic groups.

In another embodiment, the second polycarbonate is derived from bisphenol A.

B. Branching agent

The polycarbonate of the claimed invention contains branched polycarbonate (s). Various types of branching agents may be used in the claimed invention / inventions which are covered by this disclosure.

Branched polycarbonate blocks can be prepared by adding a branching agent during polymerization. Such branching agents include polyfunctional organic compounds containing at least three functional groups selected from hydroxyl, carboxyl, carboxylic acid anhydrides, haloformyl, and mixtures of the functional groups described above. Specific examples are trimellitic acid, trimellitic acid anhydride, trimellitic acid trichloride (TMTC), tris-p-hydroxyphenyl ethane (THPE), 3,3-bis- (4-hydroxyphenyl) Phenol TC (1,3,5-tris ((p-hydroxyphenyl) isopropyl) benzene), tris-phenol PA (also known as isatin-bis-phenol), tris- Bis (p-hydroxyphenyl) -ethyl) alpha, alpha-dimethylbenzyl) phenol), 4-chloroformyl phthalic anhydride, trimesic acid, and benzophenone tetracarboxylic acid. The branching agent may be added at a level of 0.05 to 2.0 wt%. Mixtures comprising linear polycarbonate and branched polycarbonate may be used.

In some embodiments, certain types of branching agents are used in the formation of the branched polycarbonate material. These branched polycarbonate materials have statistically more than two end groups. The branching agent is added in an amount sufficient to obtain the desired branching content, i.e., more than two end groups (as compared to the bisphenol monomer). The molecular weight of the polymer can become very high as a branching agent is added, which can lead to viscosity problems during phosgenation. Thus, in some embodiments, the amount of chain termination used during polymerization increases. The amount of chain terminator used when a particular branching agent is used is generally higher than when the chain terminator is used alone. The amount of chain termination used is generally greater than about 5 mole percent and less than 20 mole percent based on the bisphenol monomer.

In some embodiments, the branching agent is a structure derived from triacid trichloride of formula (20): < RTI ID = 0.0 >

(20)

(20)

Wherein Z is hydrogen, halogen, C _{1 -3} alkyl, C _{1 -3} alkoxy groups, C _{7 -12} aryl, alkylaryl, or nitro group, z is 0 to 3; Or a branching agent is derived from the reaction of a trisubstituted phenol of formula (21)

(21)

(21)

Where T ¹ is C _{1 -20} alkyl, C _{1 -20} alkylene group, C _{7 -12} aryl-alkyl, or alkylaryl group, S is hydrogen, halogen, C _{1 -3} alkyl, C _{1 -3} alkoxy group, C _{7 -12} aryl, alkylaryl, or a nitro group, s is 0 to 4;

In another embodiment, the branching agent is a structure having the formula (22):

(22)

(22)

Specific examples of branching agents particularly effective in such compositions include trimellitic acid trichloride (TMTC), tris-p-hydroxyphenyl ethane (THPE), and isatin-bis-phenol. In one embodiment, in formula (20), Z is hydrogen and z is 3. In another embodiment, in formula (21), S is hydrogen, T ¹ is methyl and s is 4.

The relative amount of branching agent used in the preparation of the polymer will depend on a number of considerations such as, for example, the type of R ¹ group, the amount of cyanophenol, and the desired molecular weight of the polycarbonate. In general, the amount of branching agent per 100 R ¹ of about 0.1 to 10 branching units of the, in particular R 100 ¹ per unit of about 0.5 to 8 branching units, more specifically, R ¹ 100 It is effective to provide branch units of about 0.75 to 5 per unit. For a branching agent having the formula (20), a branched-tree amount of the ester 100 R ¹ per unit of about 0.1 to 10 branching units, specifically, 100 R ¹ per unit of about 0.5 to 8 branching units, more specifically, 100 R ¹ per unit of about 0.75 To 5 tri-ester units. For a branching agent having the formula (21), minute resinous trees carbonate units amount 100 R ¹ per unit of about 0.1 to 10 branching units, specifically, 100 R ¹ per unit of about 0.5 to 8 branching units, more specifically, 100 R ¹ per unit of about 0.75 Lt; / RTI > to 5 tricarbonate units. In some embodiments, a combination of two or more branching agents may be used.

In one embodiment, the polycarbonate of the composition has a fractionation of at least about 1%, or at least about 2%, or at least about 3%, or from about 1% to about 3%.

C. End capping agent

Various types of end-capping agents can be used in the claimed invention / inventions covered by this disclosure.

In one embodiment, the end capping agent is selected based on the molecular weight of the polycarbonate and the branching profile imparted by the branching agent. A desired goal is to obtain a thin walled article having excellent flame retardancy, for example, a molded article of the composition having a UL94 VO grade at a thickness of 1 mm, 1.5 mm, 2.0 mm, or 1.0 mm to 2.0 mm.

Without wishing to be bound by theory, the pKa of the endcapping agent is critical to achieving a thin walled product with a UL94 VO rating. The pKa of the end capping agent is a measure of its relative acidity. The lower the pKa of the endcapping agent, the more acidic the endcapping agent. Unexpectedly, it was observed that the pKa of the end capping agent was an indicator of the flame retardancy of the branched polycarbonate. For example, low pKa for branched polycarbonate provides better flame retardancy than high pKa.

In one embodiment, the end capping agent has a pKa of about 8.3 to about 11. In another embodiment, the end capping agent has a pKa of from 9 to 11.

In another embodiment, the end capping agent is selected from one or more of the following: phenols or phenols containing at least one substituent having at least one of the following: an aliphatic group, an olefin group, an aromatic group, a halogen, an ester group, group.

In another embodiment, a commercially particularly useful endcapping agent is selected from one or more of the following: phenol, para-t-butylphenol or para-cumylphenol.

D. Additives for end-capped polycarbonate compositions

Various types of flame retardants may be used in the claimed invention / inventions covered by this disclosure.

In one embodiment, the flame retardant additive is selected from the group consisting of, for example, potassium perfluorobutanesulfonate (Rimar salt), potassium perfluorooctanesulfonate, tetraethylammonium perfluorohexanesulfonate, potassium diphenylsulfonesulfonate Flame retarding salts such as the alkali metal salts of perfluorinated C _1-16 alkyl sulfonates such as, for example, And inorganic acid complexes such as Na ₂ CO ₃ , K ₂ CO ₃ , MgCO ₃ , CaCO ₃ , CaCO ₃ , CaCO ₃ , and oxo, such as alkali metal and alkaline earth metal salts of carbonic acid, such as BaCO ₃ - anion complex, or _{Li 3 AlF 6, BaSiF 6,} KBF 4, K 3 AlF 6, KAlF 4, K 2 SiF 6, and / or Na ₃ fluoroalkyl, such as AlF ₆ - include salts formed by reaction with an anion complex. Rimar salts and KSS are particularly useful in the polycarbonate compositions disclosed herein alone or in combination with other flame retardants.

In other embodiments, the flame retardant is selected from one or more of the following: a perfluorinated C _{1 -16} alkali metal salt of an alkyl sulfonate; Potassium perfluorobutanesulfonate; Potassium perfluorooctanesulfonate; Tetraethylammonium perfluorohexanesulfonate; And potassium diphenylsulfonesulfonate.

In another embodiment, the flame retardant is not a bromine or chlorine containing composition.

In another embodiment, the flame-retardant additive comprises an organic compound comprising phosphorus, bromine, and / or chlorine. For regulatory reasons, non-brominated and non-chlorinated phosphorus-containing flame retardants may be used in certain applications, for example organic phosphates and phosphorus-nitrogen bond containing organic compounds. One type of exemplary organic phosphate is an aromatic phosphate of the formula (GO) ₃ P = O, wherein each G is independently an alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl group, Aromatic group. Two of the groups G may be joined together to provide a ring group such as, for example, diphenyl pentaerythritol diphosphate. Exemplary aromatic phosphates include, but are not limited to, phenylbis (dodecyl) phosphate, phenylbis (neopentyl) phosphate, phenylbis (3,5,5'-trimethylhexyl) phosphate, ethyldiphenylphosphate, ) Phosphate, bis (2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate, bis , 2-chloroethyl diphenyl phosphate, p-tolylbis (2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate and the like. Specific aromatic phosphates are those in which G is an aromatic group, for example, triphenyl phosphate, tricresyl phosphate, isopropylated triphenyl phosphate, and the like.

Bifunctional or multifunctional aromatic phosphorus-containing compounds are also useful, for example, compounds of the formula:

Wherein G ¹ each independently represent a hydrocarbon group having 1 to 30 carbon atoms and; G ² is each independently a hydrocarbon or hydrocarbonoxy having 1 to 30 carbon atoms; X ¹ is each independently bromine or chlorine; n is from 0 to 4 and m is from 1 to 30. Exemplary bifunctional or multifunctional aromatic phosphorus-containing compounds include resorcinol tetraphenyl diphosphate (RDP), bis (diphenyl) phosphate of hydroquinone and bis (diphenyl) phosphate of bisphenol A, their respective oligomers and Polymer-compatible water, and the like. X ^a represents a single bond, C _{3 -20} cycloalkylidene, or one of the above-mentioned formulas (5) or (6).

Exemplary flame retarding additives containing phosphorus-nitrogen bonds include phosphonitrile chloride, phosphorus ester amide, phosphoric acid amide, phosphonic acid amide, phosphinic acid amide, tri (aziridinyl) phosphine oxide.

Halogenated organic flame retardant compounds may also be used as flame retardants, for example halogenated flame retardant compounds of formula (26)

(26)

(26)

Where R is a C _{1 -36} alkylene, alkylidene or alkylene such as, for example, methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, An alicyclic bond; Or an oxygen ether, a carbonyl, an amine or a sulfur containing bond such as, for example, a sulfide, a sulfoxide, a sulfone, or the like; R may also be composed of two or more alkylene or alkylidene linkages connected by groups such as aromatic, amino, ether, carbonyl, sulfide, sulfoxide, sulfone and the like.

Ar and Ar 'in formula (26) are each independently a mono- or polycyclic aromatic group such as phenylene, biphenylene, terphenylene, naphthylene and the like.

When present, each X is independently a monovalent hydrocarbon group, for example, an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, decyl and the like; Aryl groups such as phenyl, naphthyl, biphenyl, xylyl, tolyl and the like; And aralkyl groups such as benzyl, ethylphenyl and the like; Cyclopentyl, cyclohexyl, and the like. The monovalent hydrocarbon group may itself contain an inert substituent.

Y is an organic, inorganic or organometallic radical, for example, (1) a halogen such as chlorine, bromine, iodine, fluorine or (2) an ether group of the formula OB wherein B is a monovalent hydrocarbon group Or (3) a monovalent hydrocarbon group of the type represented by R, or (4) other substituents such as, for example, nitro, cyano, and the like, wherein the substituents are substantially the same or different if they have one or more, It is inert.

d is each independently a maximum value equivalent to the number of replaceable hydrogens substituted on the aromatic ring containing from 1 to Ar or Ar '. e are each independently the maximum value equivalent to the number of substitutable hydrogen from 0 to R phase. Each of a, b, and c is independently an integer including 0 independently. If b is nonzero, neither a nor c can be zero. Otherwise, either a or c may be zero, but neither can be zero. When b is 0, the aromatic groups are connected directly by a carbon-carbon bond.

The hydroxyl and Y substituents on the aromatic groups Ar and Ar 'may be replaced by ortho, meta or para positions on the aromatic ring, and these groups may be in any possible geometric relationship with respect to each other.

Bisphenols are included within the ranges of the above formulas and are representative of: 2,2-bis- (3,5-dichlorophenyl) -propane; Bis- (2-chlorophenyl) -methane; Bis (2,6-dibromophenyl) -methane; 1,1-bis- (4-iodophenyl) -ethane; 1,2- bis- (2,6-dichlorophenyl) -ethane; 1,1-Bis- (2-chloro-4-iodophenyl) ethane; 1,1-Bis- (2-chloro-4-methylphenyl) -ethane; 1,1-bis- (3,5-dichlorophenyl) -ethane; 2,2-bis- (3-phenyl-4-bromophenyl) -ethane; 2,6-bis- (4,6-dichloronaphthyl) -propane; 2,2-bis- (2,6-dichlorophenyl) -pentane; 2,2-bis- (3,5-dibromophenyl) -hexane; Bis- (4-chlorophenyl) -phenyl-methane; Bis- (3,5-dichlorophenyl) -cyclohexylmethane; Bis- (3-nitro-4-bromophenyl) -methane; Bis- (4-hydroxy-2,6-dichloro-3-methoxyphenyl) -methane; And 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane 2,2- bis- (3-bromo-4-hydroxyphenyl) -propane. Also, the chemical formulas of the above structures include: 1,3-dichlorobenzene, 1,4-dibromobenzene, 1,3-dichloro-4-hydroxybenzene and 2,2'-dichlorobiphenyl, poly Dibromobiphenyl bromide, 2,4'-dibromobiphenyl and 2,4'-dichlorobiphenyl, as well as decabromodiphenyl oxide.

Another class of useful flame retardants is the class of cyclic siloxanes having the formula (R ₂ SiO) _y wherein R is a monovalent hydrocarbon or fluorinated hydrocarbon having from 1 to 18 carbon atoms and y is a number from 3 to 12. Examples of fluorinated hydrocarbons include, but are not limited to, 3-fluoropropyl, 3,3,3-trifluoropropyl, 5,5,5,4,4,3,3-heptafluoropentyl, fluoro Phenyl, difluorophenyl, and trifluorotolyl. Examples of suitable cyclic siloxanes include, but are not limited to, octamethylcyclotetrasiloxane, 1,2,3,4-tetramethyl-1,2,3,4-tetravinylcyclotetrasiloxane, 1,2,3,4- 4-tetramethyl-1,2,3,4-tetraphenylcyclotetrasiloxane, octaethylcyclotetrasiloxane, octapropylcyclotetrasiloxane, octabutylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, Tetradecamethylcycloheptasiloxane, hexadecamethylcyclooctasiloxane, eicosamethylcyclodecasiloxane, octaphenylcyclotetrasiloxane, and the like. A particularly useful cyclic siloxane is octaphenylcyclotetrasiloxane.

When present, the flame retardant additive is present in an amount of generally from 0.01 to 10% by weight, more specifically from 0.02 to 5% by weight, based on 100 parts by weight of the polymer component in the thermoplastic composition.

In other embodiments, the thermoplastic composition may further comprise an impact modifier (s), provided that the additive is chosen so as not to have a significant adverse effect on the desired properties of the thermoplastic composition. Suitable impact modifiers are typically high molecular weight elastomeric materials derived from olefins, monovinyl aromatic monomers, acrylic and methacrylic acids and their ester derivatives, as well as conjugated dienes. The polymer formed from the conjugated diene may be completely or partially hydrogenated. The elastomeric material may be in the form of a homopolymer or a copolymer comprising random, block, radial block, graft and core-shell copolymer. Combinations of impact modifiers may be used.

Specific types of impact modifiers include (i) a glass transition temperature (T _g ) of less than 10 ° C, more specifically a glass transition temperature of less than -10 ° C, or more specifically of -40 ° C to -80 ° C (Ii) an elastomer-modified graft copolymer comprising a rigid polymer superstrate grafted onto an elastomeric polymer substrate. Suitable materials for use in the elastomeric phase include, for example, conjugated diene rubbers such as polybutadiene and polyisoprene; Copolymers of conjugated dienes having less than 50% by weight of copolymerizable monomers such as, for example, monovinyl compounds such as styrene, acrylonitrile, n-butyl acrylate, or ethyl acrylate; Olefin rubbers such as ethylene propylene copolymer (EPR) or ethylene-propylene-diene monomer rubber (EPDM); Ethylene-vinyl acetate rubbers; Silicone rubber; Elastomeric C _{1 -8-alkyl} (meth) acrylate; C _{1 -8-alkyl} (meth) acrylates with butadiene and / or elastomeric copolymer of styrene; Or combinations comprising at least one of the foregoing elastomers. Suitable materials for use as the hard phase include, for example, monovinyl aromatic monomers such as styrene and alpha-methylstyrene, and C _1-6 esters of acrylonitrile, acrylic acid, methacrylic acid and acrylic acid and methacrylic acid, And specifically includes monovinyl monomers such as methyl methacrylate. The term " (meth) acrylate " as used herein includes both acrylate and methacrylate groups.

Exemplary elastomeric modified graft copolymers include styrene-butadiene-styrene (SBS), styrene-butadiene rubber (SBR), styrene-ethylene-butadiene-styrene (SEBS), ABS (acrylonitrile-butadiene- (AES), styrene-isoprene-styrene (SIS), methyl methacrylate-butadiene-styrene (MBS), and styrene-acrylonitrile do.

The impact modifier, if present, is generally present in an amount of from 1 to 30% by weight, based on 100 parts by weight of the polymer component in the thermoplastic composition.

In addition to the end-capped polycarbonate and flame retardant (and optional impact modifier if used), the thermoplastic composition may include various additives conventionally incorporated into this type of polycarbonate composition, including additives such as transparency and flame retardancy But only if it is chosen so as not to have a significant adverse effect on the desired properties of the same polycarbonate. Combinations of additives may be used. Such additives may be mixed at the appropriate time during mixing of the ingredients to form the composition. A variety of additives may be incorporated into the compositions of matter contained by the presently claimed / claimed invention.

In one embodiment, at least one additive from one or more of the following is selected: a UV stabilizing additive, a thermal stabilizing additive, a release agent, a colorant, an organic filler and an inorganic filler, and a gamma-stabilizer.

Possible fillers or reinforcing agents include, for example, silicates such as aluminum silicate (mullite), synthetic calcium silicate, zirconium silicate, fused silica, crystalline silica graphite, natural silica and the like, and silica powders; Boron powder such as boron-nitride powder, boron-silicate powder and the like; Oxides such as TiO ₂ , aluminum oxide, magnesium oxide and the like; Calcium sulfate (as its anhydride, dihydrate or trihydrate); Calcium carbonate such as chalk, lime, marble, synthetic precipitated calcium carbonate and the like; Talc, including fibrous, modular, acicular, lamellar talc, and the like; Wollastonite; Surface treated wollastonite; Glass spheres such as hollow and solid glass spheres, silicate spheres, cenosphere, aluminosilicates (armosphere) and the like; Kaolin including hard kaolin, soft kaolin, fired kaolin, kaolin including various coatings known in the art for promoting compatibility with the polycarbonate polymer matrix; Monofilament fibers or "whiskers" such as silicon carbide, alumina, boron carbide, iron, nickel, copper and the like, asbestos, carbon fibers, glass fibers such as E, A, C, ECR, R, S, D or NE glasses Barium compounds such as barium titanate, barium ferrite, barium sulfate, heavy spar, and the like; particulate or fibrous aluminum, bronze, and the like, Flake fillers such as glass flakes, flake silicon carbide, aluminum diboride, aluminum flakes, steel flakes, etc., fibrous fillers such as one or more aluminum silicates, aluminum oxides, magnesium oxide Inorganic staple fibers such as those derived from blends including calcium sulfate hemi-hydrate and the like; Natural fillers and reinforcing agents such as wood pulp, cellulose, cotton, sisal, jute, starch, coke, lignin, polished nut shells, corn, rice bran, etc .; fibrous products such as polytetrafluoro An organic filler such as ethylene, an organic filler such as poly (ether ketone), polyimide, polybenzoxazole, poly (phenylene sulfide), polyester, polyethylene, aromatic polyamide, aromatic polyimide, polyetherimide, polytetrafluoroethylene Clay, feldspar, flue dust, fillite, quartz, quartzite, perlite, and the like, as well as reinforcing organic fiber fillers formed from organic polymers capable of forming fibers such as acrylic resins, poly (vinyl alcohol) ), Tripoli, diatomaceous earth, carbon black, and the like, or combinations comprising at least one of the foregoing fillers or reinforcing agents .

The filler and reinforcing agent may be coated with a layer of a metal material to promote conductivity, or may be surface treated with a silane to improve adhesion and dispersibility with the polycarbonate polymer matrix. The reinforcing filler may also be provided in the form of monofilament or multifilament fibers and may be used alone or in combination with other types of fibers such as co-weaving or core / sheath / sheath), side-by-side, orange-type or matrix and fibril constructions, or by other methods known to those skilled in the art of fiber production. Exemplary public domain constructions include, for example, glass fiber-carbon fiber, carbon fiber-aromatic polyimide (aramid) fiber, and aromatic polyimide fiber glass fiber. Fibrous fillers include, for example, rovings such as 0-90 degree fabrics, woven fibrous reinforcements; Continuous strand mat, cut strand mat, tissue, paper and felt, and the like; Or in the form of a three-dimensional reinforcing agent such as a braid. The filler is generally used in an amount of 0 to 80 parts by weight based on 100 parts by weight of the polymer component in the composition.

Exemplary antioxidant additives include, for example, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite ("IRGAFOS 168" Di-t-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite and the like; Alkylated monophenols or polyphenols; Alkylation reaction products of polyphenols and dienes such as tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane and the like; The butylation reaction product of para-cresol or dicyclopentadiene; Alkylated hydroquinone; Hydroxylated thiodiphenyl ether; Alkylidene-bisphenol; Benzyl compounds; Esters of beta - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with monohydric or polyhydric alcohols; Esters of beta - (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with monohydric or polyhydric alcohols; (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, dodecyldithiopropionate, ditridecylthiodipropionate, octadecyl-3- Esters of thioalkyl or thioaryl compounds such as pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and the like; Amide such as beta - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, or a combination comprising at least one of the above-mentioned antioxidants. The antioxidant is generally used in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the polymer component in the thermoplastic composition (excluding the filler).

Exemplary passivating additives include, for example, organophosphites such as triphenyl phosphite, tris- (2,6-dimethylphenyl) phosphite, tris- (mixed mono- and di-nonylphenyl) phosphite, and the like; Phosphonates such as dimethylbenzene phosphonate and the like, phosphates such as trimethyl phosphate and the like, or combinations comprising at least one of the above-mentioned heat stabilizers. The heat stabilizer is generally used in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the polymer component in the thermoplastic composition.

Light stabilizers and / or ultraviolet (UV) absorbing additives may also be used. Exemplary photostabilizing additives include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy- -4-n-octoxybenzophenone, and the like, or a combination comprising at least one of the above photostabilizers. The photostabilizer is generally used in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the polymer component in the thermoplastic composition.

Exemplary UV absorbing additives include, for example, hydroxybenzophenone; Hydroxybenzotriazole; Hydroxybenzotriazine; Cyanoacrylate; Oxanilide; Benjazinon; 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) -phenol (CYASORB * 5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB * 531); 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) -phenol (CYASORB * 1164); 2,2 '- (1,4-phenylene) bis (4H-3,1-benzoxazin-4-one) (CYASORB * UV-3638); Bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [ Methyl] propane (UVINUL * 3030); 2,2 '- (1,4-phenylene) bis (4H-3,1-benzoxazin-4-one); Bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [ Methyl] propane; Nano-sized inorganic materials such as titanium oxide, cerium oxide, and zinc oxide, all of which have a particle size of about 100 nm or less; Etc., or combinations comprising at least one of the foregoing UV absorbers. The UV absorber is generally used in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the polymer component in the thermoplastic composition.

Plasticizers, lubricants, and / or mold release agents may also be used. Some of these types of materials are quite redundant and include, for example, phthalic acid esters such as dioctyl-4,5-epoxy-hexahydrophthalate; Tris- (octoxycarbonylethyl) isocyanurate; Tristearin; Bifunctional or multifunctional aromatic phosphates such as resorcinol tetraphenyl diphosphate (RDP), hydroquinone bis (diphenyl) phosphate and bis (diphenyl) phosphate of bisphenol A; Poly-alpha-olefins; Epoxidized soybean oil; Silicon oils including silicone oils; Examples of esters include fatty acid esters such as alkyl stearyl esters such as methyl stearate, stearyl stearate, pentaerythritol tetrastearate (PETS) and the like; Hydrophilic and hydrophobic nonionic surfactants comprising methyl stearate and a combination comprising at least one of a polyethylene glycol polymer, a polypropylene glycol polymer, a poly (ethylene glycol-co-propylene glycol) copolymer, As a combination, for example, a combination of methyl stearate and a polyethylene-polypropylene glycol copolymer in a suitable solvent; Waxes, montan waxes, paraffin waxes and the like. Such materials are generally used in an amount of 0.001 to 1 part by weight, specifically 0.01 to 0.75 parts by weight, more specifically 0.1 to 0.5 parts by weight, based on 100 parts by weight of the polymer component in the thermoplastic composition.

The term " antistatic agent " refers to a monomeric, oligomeric or polymeric material that can be processed into a polymeric resin and / or sprayed onto a material or article to improve the conductive and overall physical performance. Examples of monomeric antistatic agents include glycerol monostearate, glycerol distearate, glycerol tristearate, ethoxylated amines, primary, secondary and tertiary amines, ethoxylated alcohols, alkyl sulfates, alkylaryl sulfates, alkyl phosphates , Alkylammonium salts such as alkylamine sulfates, sodium stearylsulfonate, sodium dodecylbenzenesulfonate and the like, quaternary ammonium salts, quaternary ammonium resins, imidazoline derivatives, sorbitan esters, ethanol amides, betaines or the like And combinations comprising at least one of the foregoing monomeric antistatic agents.

Exemplary polymeric antistatic agents include certain polyester amides, polyether-polyamide (polyetheramide) block copolymers, polyetherester amide block copolymers, polyether esters or polyurethanes, each of which may be a polyethylene glycol, a poly Propylene glycol, polytetramethylene glycol, and the like. The term " polyalkylene glycol moiety polyalkylene oxide unit " Such polymeric antistatic agents are, for example, commercially available PELESTAT * 6321 (Sanyo) or PEBAX * MH1657 (Atofina), IRGASTAT * P18 and P22 (Ciba-Geigy). Other polymeric materials that can be used as antistatic agents are essentially conductive polymers such as polyaniline (commercially available as PANIPOL * EB from Panipol), polypyrrole and polythiophene (commercially available from Bayer) Lt; RTI ID = 0.0 > conductivity < / RTI > In one embodiment, a combination comprising carbon fibers, carbon nanofibers, carbon nanotubes, carbon black, or one or more of the foregoing is used in a polymeric resin containing a chemical antistatic agent to electrostatically cure the composition It can be acidic (dissipative). The antistatic agent may generally be used in an amount of 0.0001 to 5 parts by weight based on 100 parts by weight of the polymer component of the thermoplastic composition.

Colorants such as pigments and / or dye additives may also be present provided they do not adversely affect the flame retardant performance. Useful pigments include, for example, metal oxides and mixed metal oxides such as zinc oxide, titanium dioxide, iron oxide and the like as inorganic pigments; Sulfides such as zinc sulfide and the like; Aluminate; Sodium sulfo-silicate sulphates, chromates and the like; Carbon black; Zinc ferrite; Ultra marine blue; Examples of the organic pigments include pigments such as azo, diazo, quinacridone, perylene, naphthalene tetracarboxylic acid, flavanthrone, isoindolinone, tetrachloroisoindolinone, anthraquinone, entrone, dioxazine, phthalocyanine, and Azo lake; Pigment Red 101; Pigment Red 163, Pigment Yellow 163, Pigment Yellow 163, Pigment Red 163, Pigment Red 163, Pigment Red 163, Pigment Red 173, Brown 24; Or combinations comprising at least one of the foregoing pigments. The pigment is generally used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the polymer component in the thermoplastic composition.

Exemplary dyes may be organic in nature and include, for example, coumarin dyes such as coumarin 460 (blue), coumarin 6 (green), nile red and the like; Lanthanide complex; Hydrocarbons and substituted hydrocarbon dyes; Polycyclic aromatic hydrocarbons dyes; Scintillation dyes such as oxazole or oxadiazole dyes; Aryl or heteroaryl-substituted poly (C _{2 -8)} olefin dyes; Carbocyanine dyes; Indanthrone dyes; Phthalocyanine dyes; Jade photographic dyes; Carbostyril dyes; Naphthalene tetracarboxylic acid dyes; Porphyrin dyes; Bis (styryl) biphenyl dyes; Acridine dyes; Anthraquinone dyes; Dyes; Methine dyes; Aryl methane dyes; Azo dyes; Indigo dyes, thioindigoid dyes, diazonium dyes; Nitro dyes; Quinone imine dyes; Aminoketone dyes; Tetrazolium dyes; Thiazole dyes; Perylene dye; Perynone dyes; Bis-benzoxazolyl thiophenes (BBOT); Triarylmethane dyes; Xanthene dyes; Thioxanthene dyes; Naphthalimide dyes; Lactone dyes; Fluorophores such as anti-stoke shift dyes which absorb at near infrared wavelengths and emit at visible wavelengths; Luminescent dyes such as 7-amino-4-methylcoumarin; 3- (2'-benzothiazolyl) -7-diethylaminocoumarin; 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole; 2,5-bis- (4-biphenyl) -oxazole; 2,2'-dimethyl-p-quaterphenyl;2,2-dimethyl-p-terphenyl; 3,5,3 "", 5 ""-tetra-t-butyl-p-quinquiphenyl;2,5-diphenylfuran;2,5-diphenyloxazole;4,4'-diphenylstilbene; 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran; 1,1'-diethyl-2,2'-carbocyanine iodide; 3,3'-diethyl-4,4 ', 5,5'-dibenzothiatricarbocyanine iodide; 7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2; 7-dimethylamino-4-methylquinolone-2; 2- (4- (4-dimethylaminophenyl) -1,3-butadienyl) -3-ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate; 2- (1-naphthyl) -5-phenyloxazole; 2,2'-p-phenylene-bis (5-phenyloxazole); Rhodamine 700; Rhodamine 800; Pyrene; Chrysene; Rubrene; Coronene and the like; Or combinations comprising at least one of the foregoing dyes. The dye is generally used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the polymer component in the thermoplastic composition.

If foams are desired, useful blowing agents include, for example, halohydrocarbons that generate low boiling halohydrocarbons and carbon dioxide; As the foaming agent which is solid at room temperature and generates gas such as nitrogen, carbon dioxide or ammonia gas when heated to a temperature higher than the decomposition temperature, for example, azodicarbonamide, a metal salt of azodicarbonamide, 4,4'-oxybis (Benzene sulfonyl hydrazide), sodium bicarbonate, ammonium carbonate, etc., or a combination comprising at least one of the foregoing blowing agents. The foaming agent is generally used in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the polymer component in the thermoplastic composition.

A drip inhibitor may also be used in the thermoplastic composition, for example, a fibril-forming fluoropolymer or a bifibril-forming fluoropolymer such as polytetrafluoroethylene (PTFE). The anti-drip agent may be encapsulated, for example, by a hard copolymer such as a styrene-acrylonitrile copolymer (SAN) as described above. PTFE encapsulated within a SAN is known as TSAN. The encapsulated fluoropolymer may be prepared by polymerizing the encapsulated polymer in the presence of a fluoropolymer, for example, an aqueous dispersion. TSAN can provide significant advantages over PTFE in that it can be more easily dispersed in the composition. An exemplary TSAN can comprise 50 wt% PTFE and 50 wt% SAN based on the total weight of the encapsulated fluoropolymer. The SAN may comprise, for example, 75 wt% styrene and 25 wt% acrylonitrile, based on the total weight of the copolymer. Alternatively, the fluoropolymer may be pre-blended in any manner with a second polymer such as, for example, an aromatic polycarbonate or SAN to form a flocculent material that can be used as a drip inhibitor. Either method can be used to prepare the encapsulated fluoropolymer. The anti-drip agent is generally used in an amount of 0.1 to 5% by weight based on 100 parts by weight of the polymer component in the thermoplastic composition.

A radiation stabilizer, specifically a gamma-radiation stabilizer, may also be present. Exemplary gamma-radiation stabilizers include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, meso-2,3-butanediol, 1,2- Alkylene polyols such as 3-pentanediol, 1,4-pentanediol, 1,4-hexanediol and the like; Cycloalkylene polyols such as 1,2-cyclopentanediol, 1,2-cyclohexanediol and the like; 2,3-dimethyl-2,3-butanediol (pinacol), and the like, as well as alkoxy-substituted cyclic or acyclic alkanes. Unsaturated alkenols are also useful and examples thereof include 4-methyl-4-penten-2-ol, 3-methyl-penten- Dimethyl-4-phen-2-ol, and 9-decen-1-ol, and also having at least one hydroxy substituted tertiary carbon, such as 2-methyl- Methyl-2-butanone, 2-phenyl-2-butanol and the like, and 1-hydroxy-1-methyl- And cyclic tertiary alcohols such as cyclohexane. Any hydroxymethylaromatic compound having a hydroxy substituent on the saturated carbon attached to the unsaturated carbon in the aromatic ring may also be used. The hydroxy substituted saturated carbon can be a methylol group (-CH2OH), or as a member of a more complex hydrocarbon group, for example, -CR4HOH or -CR24OH, wherein R4 is a complex or simple hydrocarbon. Specific hydroxymethyl aromatic compounds include benzhydrol, 1,3-benzenedimethanol, benzyl alcohol, 4-benzyloxybenzyl alcohol and benzyl benzyl alcohol. 2-methyl-2,4-pentanediol, polyethylene glycol, and polypropylene glycol are often used in gamma-radiation stabilization. The gamma-radiation stabilizing compound is typically used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the polymer component in the thermoplastic composition.

The thermoplastic composition comprising the end-capped polycarbonate and the flame retardant can be prepared in a variety of ways. For example, first the end-capped polycarbonate, flame retardant, impact modifier (if present), and / or other optional components are blended in a HENSCHEL-Mixer * high speed mixer. Other low shear treatments, including but not limited to hand mixing, may also perform such blending. The blend is then injected through a hopper into the throat of a single or biaxial extruder. Alternatively, one or more components may be incorporated into the composition by feeding directly to the extruder at the inlet and / or downstream at the side stuffer. The additive may also be compounded into the master batch with the desired polymeric resin and fed into the extruder. The extruder is typically operated at a temperature higher than the temperature required to flow the composition. The extrudate is quenched in a water bath and pelletized. The pellets produced by cutting the extrudate may be as much as 1/4 inch in length or less as desired. These pellets can then be used for shaping or forming or molding.

According to the foregoing several embodiments, the high-temperature initiation of crosslinking can be controlled by adding an alkali metal salt of the terminal by adjusting the molecular weight of the EO-capped polycarbonate or a specific flame-retardant salts, especially perfluorinated C _{1 -16} alkyl sulfonates have. In one embodiment, the addition of an inorganic flame retardant (e.g., KSS) increases the initiation temperature of the crosslinking / branching in the polycarbonate from 20 to 80 캜, specifically from 40 to 60 캜.

A shaped or shaped article comprising a thermoplastic composition is also provided. The thermoplastic composition can be molded into articles of useful shape by a variety of methods such as injection molding, extrusion, rotary molding, foam molding and thermoforming to produce handheld articles such as, for example, office machines such as computer and monitor housings, Electronic appliances, electrical connectors, and parts of lighting fixtures and articles such as ornaments, appliances, roofs, greenhouses, solariums, swimming pool enclosures and the like. The compositions are particularly useful for the manufacture of thin wall articles such as housings for electronics. Additional examples of articles that can be molded from the composition include electronic communication components such as electronic components such as relays and enclosures, components for laptops, desktops, docking stations, PDAs, digital cameras, desktops, and base station terminals .

E. Polycarbonate synthesis process

Polycarbonates can be prepared by processes such as interfacial polymerization or melt polymerization. Although the reaction conditions for the interfacial polymerization can vary, the exemplary process generally involves dissolving or dispersing the dihydric phenol reactant in aqueous caustic soda or potash, separating the resulting mixture into a water immiscible solvent To the medium, and contacting the reactant with a carbonate precursor under controlled pH conditions, for example, from 8 to 11, in the presence of a catalyst such as, for example, triethylamine or a phase transfer catalyst. Most commonly used water immiscible solvents include methylene chloride, 1,2-dichloroethane, chlorobenzene, toluene and the like.

Exemplary carbonate precursors include, for example, carbonyl halides such as carbonyl bromide or carbonyl chloride, or bishaloformates of dihydric phenols (e.g., bischloroformates such as bisphenol A, hydroquinone) or glycols (E.g., bisallylformates such as ethylene glycol, neopentyl glycol, polyethylene glycol, and the like). Combinations comprising one or more of the types of carbonate precursors described above may also be used. In one exemplary embodiment, the interfacial polymerization to form the carbonate linkages uses phosgene as the carbonate precursor, which is referred to as the phosgenation reaction.

Formula of the phase transfer catalysts that can be used (R ⁵⁾ _4, and a catalyst of the Q + X ^2, wherein R ⁵ is independently C _{1 -10} alkyl group; Q is a nitrogen or phosphorus atom; X ² is a halogen atom, or C _{1 -8} alkoxy group, or C _{6 -18} aryloxy group. Exemplary phase transfer catalysts include, for example, _{[CH 3 (CH 2) 3} ] 4 NX 2, [CH 3 (CH 2) 3] 4 PX 2, [CH 3 (CH 2) 5] 4 NX 2, [CH _{3 (CH 2) 6] 4} NX 2, [CH 3 (CH 2) 4] 4 NX 2, CH 3 [CH 3 (CH 2) 3] 3 NX 2, and _{CH 3 [CH 3 (CH 2} ) 2 ] ₃ includes NX ^2, X ² is halogen, C _{1 -8} alkoxy group, or C _{6 -18} aryloxy group. In one embodiment, X < ² > is Cl or Br. An effective amount of phase transfer catalyst may be from 0.1 to 10% by weight, based on the weight of bisphenol in the phosgenation mixture. In other embodiments, an effective amount of the phase transfer catalyst may be from 0.5 to 2% by weight, based on the weight of the bisphenol in the phosgenation mixture.

Alternatively, a melt process may be used to prepare the endcapped polycarbonate. Generally, in a melt polymerization process, the polycarbonate is reacted in a molten state with a diaryl carbonate ester such as dihydroxy reactant (s) and diphenyl carbonate in a Banbury mixer, a twin-screw extruder And the like. Volatile monohydric phenol is removed by distillation from the molten reactants, and the polymer is separated into molten residues. A melting process particularly useful for the production of polycarbonates uses diaryl carbonate esters with substituents which attract electrons to aryl groups. Specific examples of useful diaryl carbonate esters having a substituent that attracts electrons include bis (4-nitrophenyl) carbonate, bis (2-chlorophenyl) carbonate, bis (4- chlorophenyl) carbonate, bis (methyl salicyl) , Bis (4-methylcarboxyphenyl) carbonate, bis (2-acetylphenyl) carboxylate, bis (4-acetylphenyl) carboxylate or combinations comprising at least one of the foregoing.

Exemplary transesterification catalysts for making polycarbonates using a melt process include acetate, carbonate, borate, borohydride, oxide, hydroxide, hydride, and alcoholate of various metals, , Alkali metals such as sodium and potassium, alkaline earth metals such as magnesium, calcium and barium and other metals such as zinc, cadmium, tin, antimony, lead, manganese, cobalt or nickel. In addition, other useful ester exchange catalysts include tetrabutylammonium hydroxide, methyltributylammonium hydroxide, tetrabutylammonium acetate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium acetate, tetrabutylphosphonium phenolate, The same basic salts of nitrogen or phosphorus. Combinations of one or more of the above are also useful.

The protocol can be adjusted to obtain the desired product within the scope of this disclosure, which can be performed without undue experimentation. In one embodiment, the desired product is a molded article of a composition having a UL94 V0 rating at a thickness of 1 mm, 1.5 mm, 2.0 mm, or about 1.0 mm to about 2.0 mm.

In one embodiment, the present invention provides a method of making an article having a UL94 V0 rating in a thickness of 1.5 mm to 2 mm, comprising the steps of: (a) providing a polycarbonate, wherein the polycarbonate Is a repeating structure of the formula (1) Background:

(1)

(One)

(Wherein at least 60% of the total number of R < ¹ > groups contain aromatic organic groups, the remainder being aliphatic, cycloaliphatic, or aromatic groups); End capping agent; And a polycarbonate comprising a branching agent; (b) a step of selecting a terminal capping agent, based on the molecular weight and the branching given by the branching agent of the polycarbonate, MVR of the polycarbonate is from about 1 to 15 cm ^3/10 min, and a terminal capping agent Wherein the pKa is from about 8.3 to about 11; (c) forming the polycarbonate containing the end capping agent and the branching agent, wherein the polycarbonate is subjected to a parallel plate melt rheology test at a heating rate of 10 DEG C / min at a temperature of from about 350 DEG C to about 450 DEG C Having a maximum melt viscosity of at least 8,000 poises, And (d) blending the flame retardant with the polycarbonate formed.

In another embodiment, the maximum melt viscosity is greater than 25,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10 占 폚 / min at a temperature of from about 350 占 폚 to about 450 占 폚.

In another embodiment, the pKa of the end capping agent is from about 8.3 to about 11.

F. Performance Characteristics

Obtaining good flame performance (UL94 V0) for thin walled articles made of polycarbonate resin (eg, less than 2 mm thick) will result in faster flame out times while avoiding flame drop during UL94 testing . Short flame decay times are generally achieved through the use of flame retardants, while the addition of anti-dripping agents such as flame-retardant polytetrafluoroethylene (PTFE) is prevented. In addition, it is particularly difficult for transparent thin wall articles to achieve excellent flame performance because the drip inhibitor, such as PTFE, makes the article translucent or opaque. Thus, in the case of transparent thin wall articles, the prevention of dropping must be achieved in other ways.

One way to reduce dropping is to increase the molecular weight of the polycarbonate resin, but this approach does not increase the molding temperature because of the reduced fluidity of the resin during molding, and without the risk of polycarbonate molecular weight deterioration and color formation, it is difficult to fill thin wall molds with flow lengths or complicated designs. Branched polycarbonate resins can provide a partial solution to the fluidity problem because the branches provide a means for entangling polycarbonate chains to reduce dropping without loss of much flow during molding. However, branched polycarbonates with high branching (1% branching or more) may be difficult to manufacture because, if the branching is too high, the polycarbonate will form a gel in the manufacturing process and often during molding . Highly branched polycarbonates are generally avoided in polycarbonate manufacture and product formulations because the gels impair the impact properties and aesthetics of transparent polycarbonate articles.

In addition, certain types of end groups attached to the ends of the branched polycarbonate chain, such as p-cyanophenol, can provide drip-resistant benefits during UL testing. However, not all branched polycarbonates are formed from p-cyanophenol end capping agents.

A common method for designing polycarbonate that provides a transparent polycarbonate formulation that is easily molded into thin wall articles by balancing the molecular weight, branching and end groups types and passes the UL94 V0 test has been found. This involves measuring the maximum melt viscosity of the polycarbonate at 350 캜 to 450 캜 during the melt rheological test. &Quot; Peak melt viscosity " is the highest melt viscosity value (unit poise) achieved at 350 ° C to 450 ° C during the rheological testing of polycarbonate resins.

When the maximum melt viscosity of the polycarbonate resin containing the branching agent and the end capping agent is 25,000 poise or more at 350 ° C to 450 ° C, the molded article produced from the resin and the flame retardant additive is consistently UL94 Pass the V0 test. When a polycarbonate resin having a maximum melt viscosity of 7,000 poise at 350 DEG C to 450 DEG C is blended with a flame retardant additive, it provides a molded article that consistently passes the UL94 V0 test at a thickness of 1.5 mm or more.

Further, after measuring the maximum melt viscosity of many polycarbonate resins having various branching points, MW (weight average molecular weight of the polycarbonate containing the terminal capping agent and the branching agent) and other types of end capping agent, A relationship was found between the map, BL (moles divided by number of bisphenol (s)), MW (by GPC using a polycarbonate standard) and pKa of the end capping agent. These relationships are represented by the following polynomial:

Maximum melt viscosity =

-57135.91 + 36961.39 * BL + 14001.13 * MW 1/3 - 46944.24 * pKa - 322.51 * BL * MW 1/3 - 2669.19 * BL * pKa + 215.83 * MW 1/3 * pKa + 1125.63 * BL 2 - 200.11 * MW ^2/3 + 2231.15 * pKa ²

Where BL is the mole ratio of branching agent in the blend, determined by dividing the number of moles of branching agent by the total number of moles of bisphenol or bisphenols in the composition, and MW is the weight average of the branching agent and the polycarbonate containing the endcapping agent Molecular weight, which is measured by gel permeation chromatography using a polycarbonate standard, and pKa is the pKa of the end capping agent.

This formula allows for a wide range of designs of polycarbonate resins to pass the UL94 V0 test at thin wall thicknesses. Designing a polycarbonate resin involves selecting the end capping agent and adjusting the molecular weight of the resin and the branching of the resin during the manufacturing process so that the calculated or measured maximum melt viscosity is, for example, 1.5 mm In case of above, it should have a high value above 7000 poise, or above 25000 poise above 1.0 mm. If the pKa of the endcapping agent has a low value (e.g., methyl-p-hydroxybenzoate with pKa 8), the amount of MW and branching required to achieve UL94 V0 performance may be reduced. If the pKa of the end capping agent has a high value (for example p-t-butylphenol with pKa 10.3), the MW and branching must be high. Also, after the end capping agent is selected, a balance between molecular weight and molecular weight can be selected during the manufacturing process. The balance between these factors can be performed without undue experimentation.

While not intending to be bound by theory, it is believed that the viscosity behavior of the polycarbonate resin containing the branching agent and the endcapping agent during the UL94 flame test, when passed through a temperature in the range of 350 DEG C to 450 DEG C, Reflects the initiation of polymerizable network formation. Polycarbonate resins that form networks of high degrees (reflected in higher maximum melt viscosities in rheological tests) appear to perform better in UL flame tests on thin walls. The higher the maximum melt viscosity value, the thinner the thin wall for UL94 V0 acceptance.

Surprisingly, blending of polycarbonate with other polycarbonates having a high maximum melt viscosity also provides a blend with good flowability and excellent flame retardant (FR) performance in thin wall thickness. The most effective polycarbonate for blending is a polycarbonate having a measured maximum melt viscosity of 25,000 poise or a calculated maximum melt viscosity of 25,000 poise or more. Thus, in one embodiment, a polycarbonate having a weight average MW of 35,526 g / mole and a calculated maximum melt viscosity of 23,923 poise is mixed with a second polycarbonate having a weight average MW of 22,999 g / mole and a ratio of 1: 1 Lt; / RTI > Rimar flame retardants, octaphenylcyclotetrasiloxane, thermal stabilizers, and release agents were also present in the blend. The blend had an MVR of 13.8 (300 DEG C / 1.2.Kg.360s). The blend showed a UL94 V0 grade at a thickness of 1.5 mm.

In one embodiment, the present invention additionally provides a composition comprising: a flame retardant; And a polycarbonate comprising the formula (1):

Wherein at least 60% of the total number of R < ¹ > groups contains aromatic organic groups and the remainder is an aliphatic, alicyclic, or aromatic group, said polycarbonate comprising at least one bisphenol; Wherein the end capping agent is not cyanophenol; Said polycarbonate comprising a branching agent; Polycarbonate containing branching agent and wherein the end capping agent is, when calculated as the maximum melt viscosity equation, have a maximum melt viscosity of at least 7,000 poise: -57135.91 + 36961.39 * BL + 14001.13 * MW 1/3 - Of ^{200.11 * MW 2/3 + 2231.15 * pKa} 2, where BL is the formulation - 46944.24 * pKa - 322.51 * BL * MW 1/3 - 2669.19 * BL * pKa + 215.83 * MW 1/3 * pKa + 1125.63 * BL 2 Branching agent, which is determined by dividing the number of moles of the branching agent by the total number of moles of bisphenol or bisphenols in the composition, MW is the weight average molecular weight of the polycarbonate containing the branching agent and the terminal capping agent, Is measured by gel permeation chromatography using a polycarbonate standard, pKa is the pKa of the endcapping agent; The molded article of the composition has a UL94 VO rating at a thickness of 1 mm, 1.5 mm, 2.0 mm, or from about 1.0 mm to about 2.0 mm.

In another embodiment, the maximum melt viscosity is greater than or equal to 25,000 as calculated by the equation above.

In another embodiment, the present invention additionally provides a method of making a product having a UL94 V0 rating in a thickness of 1.5 mm to 2 mm, comprising the steps of: (a) providing a polycarbonate, The carbonate may be represented by the formula (1):

(1)

(One)

(Wherein at least 60% of the total number of R < ¹ > groups contains aromatic organic groups and the remainder is an aliphatic, alicyclic or aromatic group, the polycarbonate containing at least one bisphenol); As the end capping agent, a non-cyanophenol end capping agent; And a polycarbonate comprising a branching agent; (b) a molecular weight and a step of selecting the terminal capping agent, based on the branching given by the branching agent, MVR is from 1 to 15 cm ^3/10 minutes to about of the polycarbonate of the polycarbonate, the terminal Wherein the pKa of the capping agent is from about 8 to about 11; (c) forming the polycarbonate containing the end capping agent and the branching agent, wherein the polycarbonate has a maximum melt viscosity of at least 7,000 poise as calculated by the following maximum melt viscosity equation: -57135.91 + 36961.39 ^{* BL + 14001.13 * MW 1/} 3 - 46944.24 * pKa - 322.51 * BL * MW 1/3 - 2669.19 * BL * pKa + 215.83 * MW 1/3 * pKa + 1125.63 * BL 2 - 200.11 * MW 2/3 + 2231.15 * pKa ² , wherein BL is the molar ratio of branching agent in the blend, determined by dividing the number of moles of branching agent by the total number of moles of bisphenol or bisphenols in the composition, MW is the weight average molecular weight of the polycarbonate formed, The molecular weight is measured by gel permeation chromatography using a polycarbonate standard, and pKa is the pKa of the end capping agent; And (d) blending the flame retardant with the polycarbonate formed.

In another embodiment, the maximum melt viscosity is greater than 25,000 poise, as calculated by the above equation.

Thin wall articles with excellent flame retardant performance are objects of claimed disclosure. One way to determine if the composition in question has good flame retardancy is to look at the UL94 grade.

In one embodiment, the molded article of the composition has a UL94 VO rating at a thickness of 1.5 mm, 2.0 mm, or 1.0 mm to 2.0 mm.

In another embodiment, the molded article of the composition has a UL94 VO rating at a thickness of 2 mm.

 In another embodiment, the molded article of the composition has a UL94 VO rating at a thickness of 1.5 mm.

In another embodiment, the molded article of the composition has a UL94 VO rating at a thickness of 1.0 mm.

In another embodiment, the molded article of the composition has a UL94 VO rating at a thickness of 1.0 mm to 2.0 mm.

The melt volume flow rate (sometimes abbreviated as " MVR ") measures the extrusion rate of a thermoplastic resin through an orifice at a preset temperature and load. The end-capped polycarbonate may have a measured under a load in 1.2㎏ 300 ℃, 0.1 to 200cm ^3/10 minutes of the MVR, specifically 1 to 100cm ^3/10 of the bun MVR. The MVR was measured according to ASTM D 1238.

In one embodiment, the polycarbonate has an approximately 3cm ^3/10 minutes or MVR. In another embodiment, the polycarbonate has a range of about 3 to about 30cm ^3/10 minutes or from about 3 to 10cm ^3/10 minutes or about 1 to about 15cm ^3/10 of the bun MVR.

The following polycarbonates included by the claimed invention / disclosure have various degrees of haze.

In one embodiment, the composition has a haze value of less than 1.5% at a thickness of 3.2 mm according to ASTM D1003.

The molecular weight of the polycarbonate containing the branching agent and the endcapping agent may vary depending on various end uses or other performance characteristics.

In one embodiment, the polycarbonate containing the branching agent and the end capping agent is from 20,000 g / mol to 40,000 g / mol, as measured by gel permeation chromatography using a polycarbonate standard.

The following embodiments are also encompassed by the claimed invention.

In one embodiment, the composition comprises: a flame retardant; And a polycarbonate comprising the formula (1):

(1)

(One)

At least 60% of the total number of R < ¹ > groups contains an aromatic organic group and the remainder is an aliphatic, alicyclic or aromatic group; The polycarbonate comprises a terminal capping agent selected from phenol or a phenol substituted with at least one alkyl group, alkoxy group, ester group, ether group or halogen; Wherein the polycarbonate comprises a branching agent selected from one or more of the following THPE, TMTC, and isatin-bis-phenol; The fraction of the polycarbonate is greater than about 1%; The molecular weight of the polycarbonate is from about 20,000 g / mole to about 40,000 g / mole; The end capping agent has a pKa of about 8.3 to about 11; Wherein the flame retardant comprises a potassium perfluorobutanesulfonate salt, and does not include a composition that optionally contains chlorine or bromine; The polycarbonate containing the branching and end capping agent has a maximum melt viscosity of greater than 8,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10 [deg.] C / min at a temperature of from about 350 [ Having; The molded article of the composition has a UL94 VO rating at a thickness of 1.0 mm, 1.5 mm, 2.0 mm, or 1.0 mm to 2.0 mm.

In another embodiment, the polycarbonate is derived from bisphenol A.

In another embodiment, the composition comprises a second polycarbonate different from the polycarbonate, wherein the second polycarbonate comprises the following repeating structure,

The second polycarbonate differs from the polycarbonate in that at least 60% of the total number of R < ¹ > groups contains aromatic organic groups, the remainder being aliphatic, alicyclic or aromatic groups.

In another embodiment, the second polycarbonate is a bisphenol A polycarbonate.

In another embodiment, the composition comprises a flame retardant and a polycarbonate containing greater than about 0.04 weight percent potassium perfluorobutanesulfonate salt, based on the total weight of the polycarbonate resin in the composition, (1) comprising:

(1)

(One)

At least 60% of the total number of R < ¹ > groups contains an aromatic organic group and the remainder is an aliphatic, alicyclic or aromatic group; Wherein the polycarbonate comprises a terminal capping agent, the terminal capping agent is not cyanophenol; Said polycarbonate comprising a branching agent; The polycarbonate comprises a branching agent and wherein the end capping agent is 20,000 g / mol to a 40,000 g / mol, MVR of the polycarbonate is from about 3 to about 10cm ^3/10 minutes, and; Said branching agent providing from about 1% to about 3% branching; The end capping agent has a pKa of from about 8.3 to about 10.2; The polycarbonate containing the branching agent and the end capping agent has a viscosity of greater than 8,000 poise or greater than 25,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10 [deg.] C / Of the maximum melt viscosity; The molded article of the composition has a UL94 VO rating at a thickness of 1.0 mm, 1.5 mm, 2.0 mm, or 1.0 mm to 2.0 mm; The haze of the molded article is less than 1.5% at 3.2 mm thickness according to ASTM D1003.

Except where noted otherwise, all thermoplastic compositions are prepared using a Werner & Pfleiderer co-rotating twin screw extruder (length / diameter (L / D) ratio = 30/1, die face) to provide good mixing between the components in the polymer composition. The composition thus obtained was immediately molded in a Husky or BOY injection molding machine according to ISO 294. It will be appreciated by those skilled in the art that the composition was compounded and molded at a temperature of from 270 to 330 < 0 > C and the method is not limited to such temperatures.

The scope, e.g., numerical values / values, recited in this disclosure will include disclosure for purposes of retaining and asserting each point within its scope, sub-ranges, and combinations thereof.

Combinations of various elements of the present disclosure may be encompassed by the present invention, for example, a combination of the elements of the dependent claim citing the same independent claim.

The invention is further illustrated by the following non-limiting examples.

Example

Al. Description of test procedures and test ingredients

The flame retardant additive and various compositions of PC are mixed together and pre-blended. Extrusion and molding are carried out under conventional polycarbonate processing conditions.

 Flammability testing was performed using the Standard Underwriters Laboratory UL94 test method (7 day condition control). We tested 20 bars, not the usual 5 bars. Prior to testing, the specimens were preliminarily conditioned in an air circulating oven at 70 ± 1 ° C for 168 hours and then cooled in a desiccator for at least 4 hours at room temperature. The specimens were removed from the desiccator and tested within 30 minutes. The average flame decay time, the standard deviation of flame decay time, and the total number of droplets were calculated and analyzed. Using statistical methods, this data was converted to the probability or "p (FTP)" that a particular combination would achieve the first VO acceptance in a 5-bar standard UL94 test. Preferably, for high confidence that the sample formulation will achieve a V0 rating in the UL94 test, the p (FTP) value will be close to 1 or 1. For any sample formulation, the p (FTP) value of less than 0.85 is considered too low to predict the UL94 rating of V0 for the formulation.

The maximum melt viscosity value of the resin sample was obtained with a dynamic rheometer using a Rheometrics ARES with a parallel plate fixture. The dynamic rheometer had a heating rate of 10 [deg.] C / min, a frequency of 3 rad / Strain amplitude and was heated with hot air. The maximum melt viscosity was determined as a graph of melt viscosity change during rheological tests as a function of temperature. The maximum absolute melt viscosity (unit Poise) was defined as the maximum melt viscosity in a graph at a temperature of about 350 ° C (after polymer softening) to about 450 ° C (before polymer deterioration) (see FIG.

Molecular weight values were determined by gel permeation chromatography (GPC), using a crosslinked styrene-divinylbenzene column and calibrated to a polycarbonate standard. GPC samples are prepared at a concentration of about 1 mg / ml and eluted at a flow rate of about 1.5 ml / min using methylene chloride as the solvent.

Flammability tests were performed according to the procedure of Underwriter's Laboratory Bulletin 94 of "Tests for Flammability of Plastic Materials, UL94." Several grades may be applied based on the burning rate, digestion time, dropping resistance capability, and whether or not the loading is combusted. Materials according to this procedure can be classified as UL94 HB, V0, V1, V2 based on the test results obtained for five samples. The criteria for each of these flammable categories are described below.

HB: In a 5 inch sample placed such that the long axis of the sample is horizontal to the flame, the burning rate of the sample is less than 3 inches per minute and the flame is extinguished before the 4 inch sample is burned.

V0: No flaming and / or smolding average duration of 10 seconds after the ignition flame is removed from the sample placed such that the major axis of the sample is at 180 degrees to the flame, absorbent cotton). The flame out time (FOT) of the five bars is the sum of the five flame extinction times, each of which is ignited twice during the maximum flame extinction time of 50 seconds.

V1: After removing the ignition flame from the sample with the long axis of the sample placed at 180 ° in the flame, the average length of the flame and / or soot does not exceed 25 seconds and none of the vertically placed samples Do not create a drop. The five bar flame extinction time is the sum of the five flame extinction times, each of which is ignited twice during the maximum flame extinction time of 250 seconds.

V2: The average time of the flame and / or soot after removal of the ignition flame from the sample placed on the long axis of the sample at 180 ° to the flame does not exceed 25 seconds, but the sample placed vertically produces a drop of the combustion particles igniting the surface do. The five bar flame extinction time is the sum of the five flame extinction times, each of which is ignited twice during the maximum flame extinction time of 250 seconds.

B1. A general method of preparing polycarbonate samples with high branching content and various end capping agents.

The experimental method described below describes a procedure for preparing a polycarbonate containing approximately 1% THPE fraction map and using methyl-p-hydroxybenzoate as the end capping agent.

The following materials were added into a 70 L CSTR (continuous stirred reactor) equipped with an overhead condenser and a recycle pump with a flow rate of 40 L / min: (a) 4,4-bis- (hydroxyphenyl) Propane (BPA) (4500 g, 19.73 mol); (b) Methyl p-hydroxybenzoate (135 g, 0.89 mol); 1,1,1-tris (4-hydroxyphenyl) ethane (THPE, 63 g, 0.2 mol); (c) Triethylamine (20 mL, 0.197 mol); (d) methylene chloride (24.3 L); (e) deionized water (10.7 L), and (f) sodium gluconate (10 g). The reaction was allowed to stir for 10 minutes and the pH was maintained at 8 to 9 by the addition of 30 wt% NaOH solution. The mixture was charged with phosgene (2708.1 g, 80 g / min, 27.37 mol). During the phosgene addition, the base (30 wt% NaOH in deionized water) was simultaneously charged to the reactor to maintain the reaction pH at 9-10. After the addition of phosgene was completed, it was purged with nitrogen gas and the organic layer was extracted. The organic extracts were washed once with dilute hydrochloric acid (HCl), then three times with deionized water. The organic layer was precipitated from methylene chloride with hot steam. Prior to analysis of the polymer, the polymer was dried in an oven at < RTI ID = 0.0 > 110 C. < / RTI > The Mw of the polycarbonate was measured to be 47,428 g / mol (based on polycarbonate standards).

In a similar manner, a branched polycarbonate having various molecular weights was prepared using another branching capillary, the other end capping agent. Experimental details of the polymers described herein are set forth in Table 1 below, where MHB is p-methyl-hydroxybenzoate, Ph is phenol, TBP is pt-butylphenol, MP is p- And PCP is p-cumylphenol.

                            Table 1

Melt viscosity peak characteristics and flame performance (expressed in both p (FTP) values and actual UL 94 test results) of polymers PC-1 through PC-9 in Table 1 are shown in Table 2 below. The maximum melt viscosity values reported in Table 2 as " melt viscosity peak " were obtained from dry polycarbonate powder, while the p (FTP) and UL94 V0 results were obtained from polycarbonate powders PC-1 to PC-9, (0.06% by weight), and a sterically hindered amine photostabilizer (0.08% by weight) and a mixture of Rimar Salt, potassium perfluorobutanesulfonate (0.08% by weight) and octaphenylcyclotetrasiloxane (0.05% by weight) From the polycarbonate barrel formed from the formulation containing the flame retardant package, which is based on 100% by weight of the polycarbonate.

                            Table 2

The molded articles from PC-1 to PC-9 exhibited excellent UL94 V0 performance at 1.5 mm. The linear polycarbonate control, which had no branch and phenolic end caps and had a MW value of 25,139 and a maximum melt viscosity value of only 6,142, failed the UL94 V0 test and had a rating of only V1 at 1.5 mm.

When the molded articles from PC-5 to PC-9 were tested at 1.0 mm, differences between the polycarbonates were observed. The PC-5, PC-6 and PC-9 failed the UL94 V0 test and had a p (FTP) value of less than 0.9 at 1.0 mm, while PC- 8 passed at 1.0 mm. PC-7 and PC-8 had higher MW (<47,000 units> 55,000) than PC-5 and PC-6 and had a higher maximum melt viscosity (<22,000 poise vs.> 25,000 poise).

C1. Maximum melt viscosity prediction equation

Predictors were needed to help design polycarbonates that consistently passed the UL94 V0 test at thin wall thicknesses. Various types of terminal capping agents (p-cyanophenol, methyl-p-hydroxybenzoate, phenol, p-methoxyphenol, pt-butylphenol, and p- cumylphenol) Polynomials were obtained on the basis of the melt viscosity peaks (units poise) of 35 different polycarbonates (and two replicates) with the highest melt viscosity data (Stat-Ease's Design-Expert * version 7.0.3). MW of the polycarbonate containing the end capping, BL (total moles of branching agent / total moles of bisphenol), end capping agent and branching agent (measured by GPC using a polycarbonate standard) ) And the pKa of the end capping agent. The above equation appears below:

Maximum melt viscosity = -57135.91 + 36961.39 * BL + 14001.13 * MW 1/3 - 46944.24 * pKa - 322.51 * BL * MW 1/3 - 2669.19 * BL * pKa + 215.83 * MW 1/3 * pKa + 1125.63 * BL 2 ^{- 200.11 * MW 2/3 +} 2231.15 * pKa 2

Model features are shown in Table 3 below:

                            Table 3

Model Features

        The coefficient of determination (R-Squared) is 0.87

        Adjusted coefficient of determination (Adgusted R-Squared) 0.82

        The predicted decision coefficient (predicted R-Squared) is 0.70

        Adequate Precision 14.34

The " predicted coefficient of determination " of 0.70 is quite consistent with the " adjusted coefficient of determination " of 0.82. &Quot; Moderate precision " is a measure of the signal to noise ratio. A ratio of greater than 4 is generally preferred. Here, the ratio of 14.34 represents a suitable signal, so this model can be used to find the design space.

The pKa values of the endcapping agent used in the model are listed in Table 4 below:

                             Table 4

end Capping agent pKa *

           p-Cyanophenol 8.2

           p-methyl-hydroxybenzoate 8.4

           Phenol 9.9

           p-t-butylphenol 10.2

           p-methoxyphenol 10.4

           p-cumylphenol 10.5

The pKa * values of all end capping agents except p-t-butylphenol and p-cumylphenol were obtained from the following references: J. AM. CHEM. SOC. 2002, 6424. The values selected by reference are listed in the S7 category of Table 3 of the reference. The pKa value of p-t-butyl phenol was obtained from the following reference: Journal of Molecular Structure: THEOCHEM 805, 2006, 31. The pKa of methyl-p-hydroxybenzoate was obtained from the following reference: Chromatographia Vol. 39, No. 5/6, September 1994. The pKa values of p-cumylphenol were calculated based on values of similar structure.

The model was used to recalculate the maximum melt viscosity value in Melt Viscosity Peak - Model (poise) in Table 2. In general, the correlation between the model and the actual maximum viscosity was excellent, especially when the measured value exceeded 20,000 poise. Above 20,000 poise, the difference between the measured melt viscosity values and the calculated melt viscosity values consistently was less than 10%.

Calculated melt viscosity peak measurements were surprisingly effective at predicting p (FTP) and UL94 V0 performance of polycarbonate PC-5, PC-6, PC-7 and PC-8 at a thickness of 1.0 mm. Polycarbonates with a calculated or measured maximum melt viscosity below about 25,000 poise failed the UL94 V0 test at 1.0 mm and showed a p (FTP) value of less than 0.9 (PC-5 and PC-6) as shown Polycarbonate having a measured or calculated maximum melt viscosity value of greater than about 25,000 poises passed the UL94 V0 test at 1.0 mm and had a p (FTP) value of 0.99 (PC-7 and PC-8) of 0.99, Respectively.

D1. Blend with high maximum viscosity polycarbonate

Polycarbonates PC-10, PC-11 and PC-12 were prepared using the method described above, which contained a 3% THPE fraction map and phenol, methyl-p-hydroxybenzoate, and p- Phenol. The values calculated from the above equation of maximum melt viscosity based on the weight percent THPE, pKa of the endcapping agent and MW of the polycarbonate are 22,960 (PC-10), 25,683 (PC-11), and 12,527 12). The blend blend with high flow polycarbonate (made by interfacial polymerization, with a p-cumyl phenol end capping agent and having a MW of 22,000 g / mol and a MVR of 25) was mixed with PC-10, PC-11 and PC-12 Lt; / RTI &gt; The blend blend, the MVR value of the blend produced, and the flame properties of the blend are shown in Table 5 below.

                          Table 5

The results in Table 5 illustrate the importance of making blends using polycarbonates with high maximum melt viscosity values in applications requiring thin-wall flame characteristics. PC-10 and PC-12 have very similar MWs (35,526 to 31,458 g / mol) from which the compounded blends have very similar MVRs (13.8 to 13.3), but the two blends have very different calculated maximum melt viscosity (PC-10 and PC-12) having a number average molecular weight (22,960 vs. 12,527). This difference appears to result in a very different flame performance of the two blends, one blend from PC-10 with a high calculated maximum melt viscosity of 22,960, passing the UL94 V0 test at 1.5 mm and a low calculation of 12,527 Other blends with PC-12 with the melt viscosity of the rejected UL94 V0 test at 1.5 mm.

Conventional implementations are provided for illustrative purposes, but the above detailed description should not be construed as limiting the scope of the present invention. Accordingly, various modifications, alterations, and alternatives may occur to those skilled in the art without departing from the spirit and scope of the invention.

In one embodiment, a composition is claimed comprising: a flame retardant; And a polycarbonate comprising the formula (1):

(1)

(One)

At least 60% of the total number of R &lt; ¹ &gt; groups contains an aromatic organic group and the remainder is an aliphatic, alicyclic or aromatic group; Wherein the polycarbonate comprises a terminal capping agent, the terminal capping agent is not cyanophenol; Said polycarbonate comprising a branching agent; Wherein the polycarbonate comprising the branching agent and the end capping agent has a maximum melt of at least 7,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10 DEG C per minute at a temperature of from about 350 DEG C to about 450 DEG C Has a viscosity; The molded article of the composition has a UL94 VO rating at a thickness of 2.0 mm.

In another embodiment, a method of making a product having a UL94 VO rating at a thickness of 1.5 mm to 2 mm, comprising the steps of: (a) providing a polycarbonate, said polycarbonate having the formula (1 ):

(1)

(One)

(Wherein at least 60% of the total number of R &lt; ¹ &gt; groups contain aromatic organic groups, the remainder being aliphatic, cycloaliphatic, or aromatic groups); As the end capping agent, a non-cyanophenol end capping agent; And a polycarbonate comprising a branching agent; (b) a molecular weight and a step of selecting the terminal capping agent, based on the branching given by the branching agent, MVR is from 1 to 15 cm ^3/10 minutes to about of the polycarbonate of the polycarbonate, the terminal The capping agent has a pKa of from about 8.3 to about 11; (c) forming the polycarbonate containing the end capping agent and the branching agent, wherein the polycarbonate is subjected to a parallel plate melt rheology test at a heating rate of 10 DEG C / min at a temperature of from about 350 DEG C to about 450 DEG C Having a maximum melt viscosity of at least 7,000 poises, And (d) blending the flame retardant with the polycarbonate formed.

In any of the foregoing embodiments, (i) the end capping agent has a pKa of about 8.3 to about 11, or a pKa of about 8.3 to about 10.2; And / or (ii) the end capping agent is selected based on the molecular weight of the polycarbonate and the branching imparted by the branching agent; And / or (iii) the end capping agent is selected from the group consisting of phenol; A phenol containing at least one substituent including an aliphatic group, an olefin group, an aromatic group, a halogen, an ester group, an ether group, or a halogen; Or a combination thereof, or, more specifically, the end capping agent comprises phenol, pt-butyl phenol, p-cumyl phenol, or combinations thereof; And / or said polycarbonate has an MVR of at least ³ cm 3/10 min; And / or (iv) said polycarbonate has a branching index of at least 1%, or at least 2%, or at least 3%; And / or (ⅴ) flame retardant is a perfluorinated C _{1 -16} alkali metal salt of an alkyl sulfonate; Potassium perfluorobutanesulfonate; Potassium perfluorooctanesulfonate; Tetraethylammonium perfluorohexanesulfonate; Potassium diphenylsulfon sulphonate; Or a combination thereof, or more specifically, the flame retardant comprises greater than about 0.04% by weight, based on the total weight of the polycarbonate resin in the composition, of a potassium perfluorobutanesulfonate salt; And / or (vi) the flame retardant does not comprise a composition containing chlorine or bromine; And / or (b) the branching agent comprises THPE, TMTC, isostin-bis-phenol, or a combination thereof; And / or (b) the polycarbonate containing a branching agent and a terminal capping agent has a weight average molecular weight of from about 20,000 g / mole to about 40,000 g / mole, as measured by gel permeation chromatography using a polycarbonate standard ; And / or (e) said polycarbonate is a homopolycarbonate derived from bisphenol or a copolycarbonate derived from at least one bisphenol; Or copolymers derived from at least one bisphenol and containing at least one aliphatic ester unit or at least one aromatic ester unit or at least one siloxane unit; And / or (x) the polycarbonate comprises a unit derived from bisphenol A; And / or the composition further comprises a second polycarbonate comprising formula (1);

(1)

(One)

Wherein the second polycarbonate is different from the polycarbonate, wherein at least 60% of the total number of R &lt; ¹ &gt; groups contains aromatic organic groups and the remainder is an aliphatic, alicyclic or aromatic group; And / or (xi) the second polycarbonate comprises a unit derived from bisphenol A; And / or (xii) said composition has a haze value of less than 1.5% at a thickness of 3.2 mm according to ASTM D1003; And / or (xii) the composition further comprises at least one additive, and more particularly the composition comprises a UV stabilizing additive, a thermally stabilizing additive, a release agent, a colorant, an organic filler, an inorganic filler, a gamma- Combinations; And / or (xiv) said polycarbonate containing said branching agent and said end capping agent has a maximum melt viscosity of at least 7000 poise or at least 25,000 poise, said maximum melt viscosity being calculated from the following equation: -57135.91 + 36961.39 * BL + 14001.13 * MW 1/3 - 46944.24 * pKa - 322.51 * BL * MW 1/3 - 2669.19 * BL * pKa + 215.83 * MW 1/3 * pKa + 1125.63 * BL 2 - 200.11 * MW ^{2/3 + 2231.15 * pKa 2} , where, BL is the molar ratio of branching agent in the formulation, which is determined by dividing the total number of moles of the bisphenol or bisphenol used in the composition the number of moles of the said basin, MW is the branching agent and the distal Wherein the weight average molecular weight of the polycarbonate containing the capping agent is measured by gel permeation chromatography using a polycarbonate standard and pKa is the pKa of the endcapping agent; The molded article of the composition has a UL94 VO rating at a thickness of 1 mm, 1.5 mm, 2.0 mm, or 1.0 mm to 2.0 mm; And / or (xv) said composition has a haze value of less than 1.5% at a thickness of 3.2 mm according to ASTM D1003; And / or (xvi) an article comprising said composition; And / or (xⅶ) said molded article has a UL94 VO rating at a thickness of 1.5 mm; And / or (xⅷ) said molded article has a UL94 VO rating at a thickness of 1.0 mm.

Claims (33)

Flame retardant; And
A composition comprising a polycarbonate comprising the formula (1):

(One)
At least 60% of the total number of R &lt; ¹ &gt; groups contains an aromatic organic group and the remainder is an aliphatic group or an alicyclic group;
Wherein the polycarbonate comprises a terminal capping agent, the terminal capping agent is not cyanophenol;
Said polycarbonate comprising a branching agent; And
Wherein the polycarbonate has a peak melt viscosity of greater than 7,000 poise when measured using a parallel plate melt rheology test at a heating rate of 10 DEG C / min at a temperature of 350 DEG C to 450 DEG C;
The molded article of the composition has UL94 VO 2.0 mm. The method according to claim 1,
Wherein the end capping agent has a pKa of from 8.3 to 11. 3. The method of claim 2,
Wherein the end capping agent has a pKa of from 8.3 to 10.2. The method according to claim 1,
Wherein the end capping agent is selected based on the molecular weight of the polycarbonate and the branching level imparted by the branching agent. The method according to claim 1,
The end capping agent is selected from the group consisting of phenol; A phenol containing at least one substituent including an aliphatic group, an olefin group, an aromatic group, a halogen, an ester group, an ether group, or a halogen; Or a combination thereof. 6. The method of claim 5,
Wherein the end capping agent comprises phenol, pt-butyl phenol, p-cumyl phenol, or a combination thereof. The method according to claim 1,
Wherein the polycarbonate has a MVR of at least ³ cm &lt; ³ &gt; / 10 min. The method according to claim 1,
Wherein the polycarbonate of the composition has a branching index of at least 1%. 9. The method of claim 8,
Wherein the polycarbonate of the composition has a branching index of at least 2%. 10. The method of claim 9,
Wherein the polycarbonate of the composition has a branching index of at least 3%. 11. The method according to any one of claims 1 to 10,
The flame retardant is a perfluorinated C _{1 -16} alkali metal salt of an alkyl sulfonate; Potassium perfluorobutanesulfonate; Potassium perfluorooctanesulfonate; Tetraethylammonium perfluorohexanesulfonate; Potassium diphenylsulfon sulphonate; Or a combination thereof. 11. The method according to any one of claims 1 to 10,
Wherein said flame retardant comprises greater than 0.04 weight percent potassium perfluorobutanesulfonate salt based on the total weight of said polycarbonate in said composition. 11. The method according to any one of claims 1 to 10,
Wherein the flame retardant does not comprise a composition containing chlorine or bromine. 11. The method according to any one of claims 1 to 10,
Wherein the branching agent comprises THPE, TMTC, isatin-bis-phenol, or a combination thereof. 11. The method according to any one of claims 1 to 10,
Wherein the polycarbonate has a weight average molecular weight of from 20,000 g / mole to 40,000 g / mole, as measured by gel permeation chromatography using a polycarbonate standard. 11. The method according to any one of claims 1 to 10,
Wherein the polycarbonate is a homopolycarbonate derived from bisphenol. 17. The method of claim 16,
Wherein the polycarbonate is a copolycarbonate derived from more than one bisphenol. 18. The method of claim 17,
Wherein the polycarbonate is derived from at least one bisphenol and is a copolymer containing at least one aliphatic ester unit or at least one aromatic ester unit or at least one siloxane unit. 17. The method of claim 16,
Wherein the polycarbonate comprises a unit derived from bisphenol A. 11. The method according to any one of claims 1 to 10,
A composition further comprising a second polycarbonate comprising the formula (1)

The second polycarbonate differs from the polycarbonate in that at least 60% of the total number of R &lt; ¹ &gt; groups contains an aromatic organic group and the remainder is an aliphatic group or an alicyclic group. 21. The method of claim 20,
Wherein the second polycarbonate comprises a unit derived from bisphenol A. 11. The method according to any one of claims 1 to 10,
Wherein the composition has a haze value of less than 1.5% at a thickness of 3.2 mm according to ASTM D1003. 11. The method according to any one of claims 1 to 10,
&Lt; / RTI &gt; further comprising at least one additive. 24. The method of claim 23,
Wherein the additive comprises a UV stabilizing additive, a thermal stabilizing additive, a release agent, a colorant, an organic filler, an inorganic filler, a gamma-stabilizing agent, or a combination thereof. 11. The method according to any one of claims 1 to 10,
Wherein said polycarbonate containing said branching agent and said end capping agent has a maximum melt viscosity of at least 7000 poise and wherein said maximum melt viscosity is calculated from the formula:
MW ^1/3 - 46944.24 * pKa - 322.51 * BL * MW ^1/3 - 2669.19 * BL * pKa + 215.83 * MW ^1/3 * pKa + 1125.63 * BL ² - 200.11 * MW ^2/3 + 2231.15 * pKa ² ,
Wherein BL is the molar ratio of branching agent in the blend, which is determined by dividing the number of moles of branching agent by the total number of moles of bisphenol or bisphenols in the composition, wherein MW is the polycarbonate containing the branching agent and the endcapping agent Wherein the weight average molecular weight is measured by gel permeation chromatography using a polycarbonate standard, wherein the pKa is the pKa of the endcapping agent; The molded article of the composition has a UL94 VO rating at a thickness of 1 mm, 1.5 mm, 2.0 mm, or 1.0 mm to 2.0 mm. 11. The method according to any one of claims 1 to 10,
Wherein the composition further comprises a thermoplastic polymer different from the polycarbonate. 11. The method according to any one of claims 1 to 10,
The molded article has a UL94 VO rating at a thickness of 1.5 mm. 11. The method according to any one of claims 1 to 10,
Wherein the molded article has a UL94 VO rating at a thickness of 1.0 mm. An article comprising the composition of any one of claims 1 to 10. A process for producing a product having a VO 94 grade in a thickness of from 1.5 mm to 2 mm,
(a) providing a polycarbonate, wherein the polycarbonate has the formula (1):

(One)
(Wherein at least 60% of the total number of R &lt; ¹ &gt; groups contain aromatic organic groups and the remainder are aliphatic or cycloaliphatic groups);
As the end capping agent, a non-cyanophenol end capping agent; And
A polycarbonate comprising a branching agent;
(b) a step of selecting the terminal capping agent, based on the molecular weight and the branching given by the branching agent of the polycarbonate, the MVR of 1 to 15 cm ^3/10 min of the polycarbonate, the end cap Wherein the pKa of the pine is from 8.3 to 11;
(c) forming the polycarbonate containing the end capping agent and the branching agent, wherein the polycarbonate is subjected to a parallel plate melt rheology test at a heating rate of 10 DEG C / min at a temperature of from 350 DEG C to 450 DEG C Having a maximum melt viscosity of at least 7,000 poise;
(d) blending the flame retardant with the polycarbonate formed; And
(e) molding the blended composition into the article. 31. The method of claim 30,
Wherein the step of forming the polycarbonate containing the end capping agent and the branching agent has a maximum melt viscosity of at least 7,000 poise and the maximum melt viscosity is calculated from the following formula:
MW ^1/3 - 46944.24 * pKa - 322.51 * BL * MW ^1/3 - 2669.19 * BL * pKa + 215.83 * MW ^1/3 * pKa + 1125.63 * BL ² - 200.11 * MW ^2/3 + 2231.15 * pKa ² ;
Wherein BL is the molar ratio of branching agent in the blend, which is determined by dividing the number of moles of branching agent by the total number of moles of bisphenol or bisphenols in the composition, wherein MW is the weight average molecular weight of the polycarbonate formed, Measured by gel permeation chromatography using a polycarbonate standard, and the pKa is the pKa of the end capping agent. 32. The method of claim 31,
Wherein the calculated maximum melt viscosity is at least 25,000 poise. A method for producing a polycarbonate composition,
(a) selecting a maximum melt viscosity based on a target UL94 rating;
(b) selecting the branching (BL), the target weight average molecular weight and the end capping agent to obtain the maximum melt viscosity, wherein the maximum melt viscosity is calculated according to the following equation:
Calculated maximum melt viscosity = -57135.91 + 36961.39 * BL + 14001.13 * MW ^1/3 - 46944.24 * pKa - 322.51 * BL * MW ^1/3 - 2669.19 * BL * pKa + 215.83 * MW ^1/3 * pKa + 1125.63 * BL ² - 200.11 * MW ^2/3 + 2231.15 * pKa ² ,
Wherein BL is determined by dividing the number of moles of branching agent by the total number of moles of dihydroxy compound from which the polycarbonate is derived and wherein MW is the weight of the polycarbonate measured by gel permeation chromatography using a polycarbonate standard Average molecular weight, and pKa is the pKa of the end capping agent); And
(c) reacting the dihydroxy compound, the end capping agent, the branching agent, and the carbonate precursor to produce the polycarbonate.

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